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[Co5Tp*4(Me2bta)6]: A Highly Symmetrical Pentanuclear Kuratowski Complex Featuring Tris(pyrazolyl)borate and Benzotriazolate Ligands The pentanuclear Co(II) complex [Co 5 Tp* 4 (Me 2 bta) 6 ] containing N-donor ligands (5,6-dimethyl benzotriazolate; Me 2 bta 6 ) and N-donor capping ligands (tris(3,5-dimethyl-1-pyrazolyl)borate; Tp*) was prepared by a simple and efficient ligand exchange reaction from [Co 5 Cl 4 (Me 2 bta) 6 ] and tetra- n -butyl ammonium tris(3,5-dimethyl-1-pyrazolyl)borate. Compared to the precursor complex [Co 5 Cl 4 (Me 2 bta) 6 ], which contains one Co(II) ion in octahedral and four Co(II) ions in tetrahedral coordination geometry, the title compound features all five Co(II) ions in an octahedral coordination environment while keeping a high complex symmetry. This results in modified properties including improved solubility and distinct magnetic behavior as compared to the precursor complex. The molecular structure and phase purity of the compound was verified by XRPD, UV–vis, ESI-MS, IR, and NMR measurements. Thermal stability of the compound was determined via TGA. The magnetic properties of here reported novel complex [Co 5 Tp* 4 (Me 2 bta) 6 ] as well as its precursor [Co 5 Cl 4 (Me 2 bta) 6 ] were examined in detail via ESR and SQUID measurements, which indicated weak anti-ferromagnetic exchange interactions between high-spin Co(II) centers at T < 20 and 50 K, respectively. Tamas W. Werner, Stephan Reschke, Hana Bunzen, Hans-Albrecht Krug von Nidda, Joachim Deisenhofer, Alois Loidl, and Dirk Volkmer, [Co5Tp*4(Me2bta)6]: A Highly Symmetrical Pentanuclear Kuratowski Complex Featuring Tris(pyrazolyl)borate and Benzotriazolate Ligands, Inorg. Chem. 2016, 55, 3, 1053–1060

The Role of Magnetic Dipole—Dipole Coupling in Quantum Single-Molecule Toroics For single-molecule toroics (SMTs) based on noncollinear Ising spins, intramolecular magnetic dipole–dipole coupling favours a head-to-tail vortex arrangement of the semi-classical magnetic moments associated with a toroidal ground state. However, to what extent does this effect survive beyond the semi-classical Ising limit? Here, we theoretically investigate the role of dipolar interactions in stabilising ground-state toroidal moments in quantum Heisenberg rings with and without on-site magnetic anisotropy. For the prototypical triangular SMT with strong on-site magnetic anisotropy, we illustrate that, together with noncollinear exchange, intramolecular magnetic dipole–dipole coupling serves to preserve ground-state toroidicity. In addition, we investigate the effect on quantum tunnelling of the toroidal moment in Kramers and non-Kramers systems. In the weak anisotropy limit, we find that, within some critical ion–ion distances, intramolecular magnetic dipole–dipole interactions, diagonalised over the entire Hilbert space of the quantum system, recover ground-state toroidicity in ferromagnetic and antiferromagnetic odd-membered rings with up to seven sites, and are further stabilised by Dzyaloshinskii–Moriya coupling. Kieran Hymas and Alessandro Soncini, The Role of Magnetic Dipole—Dipole Coupling in Quantum Single-Molecule Toroics, Magnetochemistry 2022, 8(5), 58

Spin-Electric Coupling with Anisotropy-Induced Vanishment and Enhancement in Molecular Ferroelectrics Manipulating quantum properties by electric fields using spin-electric coupling (SEC) effects promises spatial addressability. While several studies about inorganic materials showing the SEC functionality have been reported, the vastly tunable crystal structures of molecular ferroelectrics provide a range of rationally designable materials yet to be exploited. In this work, Mn2+-doped molecular ferroelectrics are chosen to experimentally demonstrate the feasibility of achieving the quantum coherent SEC effect in molecular ferroelectrics for the first time. The electric field pulse applied between Hahn-echo pulses in electron paramagnetic resonance (EPR) experiments causes controllable phase shifts via manipulating of the zero-field splitting (ZFS) of the Mn(II) ions. Detailed investigations of the aMn crystal showed unexpected SEC vanishment and enhancement at different crystal orientations, which were elucidated by studying the spin Hamiltonian and magnetic anisotropy. With the enhanced SEC efficiency being achieved (0.68 Hz m/V), this work discovers an emerging material library of molecular ferroelectrics to implement coherent quantum control with selective and tunable SEC effects toward highly scalable quantum gates. Yu-Hui Fang, Zheng Liu, Shen Zhou, Peng-Xiang Fu, Ye-Xin Wang, Zi-Yu Wang, Zhe-Ming Wang, Song Gao, and Shang-Da Jiang, Spin-Electric Coupling with Anisotropy-Induced Vanishment and Enhancement in Molecular Ferroelectrics, J. Am. Chem. Soc. 2022, 144, 19, 8605–8612

A Complete Ab Initio View of Orbach and Raman Spin–Lattice Relaxation in a Dysprosium Coordination Compound The unique electronic and magnetic properties of lanthanide molecular complexes place them at the forefront of the race toward high-temperature single-molecule magnets and magnetic quantum bits. The design of compounds of this class has so far being almost exclusively driven by static crystal field considerations, with an emphasis on increasing the magnetic anisotropy barrier. Now that this guideline has reached its maximum potential, a deeper understanding of spin-phonon relaxation mechanisms presents itself as key in order to drive synthetic chemistry beyond simple intuition. In this work, we compute relaxation times fully ab initio and unveil the nature of all spin-phonon relaxation mechanisms, namely Orbach and Raman pathways, in a prototypical Dy single-molecule magnet. Computational predictions are in agreement with the experimental determination of spin relaxation time and crystal field anisotropy, and show that Raman relaxation, dominating at low temperature, is triggered by low-energy phonons and little affected by further engineering of crystal field axiality. A comprehensive analysis of spin-phonon coupling mechanism reveals that molecular vibrations beyond the ion’s first coordination shell can also assume a prominent role in spin relaxation through an electrostatic polarization effect. Therefore, this work shows the way forward in the field by delivering a novel and complete set of chemically sound design rules tackling every aspect of spin relaxation at any temperature. Matteo Briganti, Fabio Santanni, Lorenzo Tesi, Federico Totti, Roberta Sessoli, Alessandro Lunghi, A Complete Ab Initio View of Orbach and Raman Spin–Lattice Relaxation in a Dysprosium Coordination Compound, J. Am. Chem. Soc. 2021, 143, 34, 13633–13645

A 9.2-GHz clock transition in a Lu(II) molecular spin qubit arising from a 3,467-MHz hyperfine interaction Spins in molecules are particularly attractive targets for next-generation quantum technologies, enabling chemically programmable qubits and potential for scale-up via self-assembly. Here we report the observation of one of the largest hyperfine interactions for a molecular system, Aiso = 3,467 ± 50 MHz, as well as a very large associated clock transition. This is achieved through chemical control of the degree of s-orbital mixing into the spin-bearing d orbital associated with a series of spin-½ La(II) and Lu(II) complexes. Increased s-orbital character reduces spin–orbit coupling and enhances the electron–nuclear Fermi contact interaction. Both outcomes are advantageous for quantum applications. The former reduces spin–lattice relaxation, and the latter maximizes the hyperfine interaction, which, in turn, generates a 9-GHz clock transition, leading to an increase in phase memory time from 1.0 ± 0.4 to 12 ± 1 μs for one of the Lu(II) complexes. These findings suggest strategies for the development of molecular quantum technologies, akin to trapped ion systems. Krishnendu Kundu, Jessica R. K. White, Samuel A. Moehring, Jason M. Yu, Joseph W. Ziller, Filipp Furche, William J. Evans, Stephen Hill, A 9.2-GHz clock transition in a Lu(II) molecular spin qubit arising from a 3,467-MHz hyperfine interaction, Nature Chemistry 14, 392–397 (2022) see also: Eric J. L. McInnes, Molecular spins clock in, Nature Chemistry volume 14, 361–362 (2022)

Ultra-narrow optical linewidths in rare-earth molecular crystals Rare-earth ions (REIs) are promising solid-state systems for building light–matter interfaces at the quantum level. This relies on their potential to show narrow optical and spin homogeneous linewidths, or, equivalently, long-lived quantum states. This enables the use of REIs for photonic quantum technologies such as memories for light, optical–microwave transduction and computing. However, so far, few crystalline materials have shown an environment quiet enough to fully exploit REI properties. This hinders further progress, in particular towards REI-containing integrated nanophotonics devices. Molecular systems can provide such capability but generally lack spin states. If, however, molecular systems do have spin states, they show broad optical lines that severely limit optical-to-spin coherent interfacing. Here the authors report on europium molecular crystals that exhibit linewidths in the tens of kilohertz range, orders of magnitude narrower than those of other molecular systems. The authors harness this property to demonstrate efficient optical spin initialization, coherent storage of light using an atomic frequency comb, and optical control of ion–ion interactions towards implementation of quantum gates. These results illustrate the utility of rare-earth molecular crystals as a new platform for photonic quantum technologies that combines highly coherent emitters with the unmatched versatility in composition, structure and integration capability of molecular materials. Diana Serrano, Senthil Kumar Kuppusamy, Benoît Heinrich, Olaf Fuhr, David Hunger, Mario Ruben, Philippe Goldner, Ultra-narrow optical linewidths in rare-earth molecular crystals, Nature 603, 241–246 (2022)

Ultrahard magnetism from mixed-valence dilanthanide complexes with metal-metal bonding Metal-metal bonding interactions can engender outstanding magnetic properties in bulk materials and molecules, and examples abound for the transition metals. Extending this paradigm to the lanthanides, in this article the authors report mixed-valence dilanthanide complexes (CpiPr5)2Ln2I3 (Ln is Gd, Tb, or Dy; CpiPr5, pentaisopropylcyclopentadienyl), which feature a singly occupied lanthanide-lanthanide σ-bonding orbital of 5dz2 parentage, as determined by structural, spectroscopic, and computational analyses. Valence delocalization, wherein the d electron is equally shared by the two lanthanide centers, imparts strong parallel alignment of the σ-bonding and f electrons on both lanthanides according to Hund’s rules. The combination of a well-isolated high-spin ground state and large magnetic anisotropy in (CpiPr5)2Dy2I3 gives rise to an enormous coercive magnetic field with a lower bound of 14 tesla at temperatures as high as 60 kelvin. COLIN A. GOULD, RANDALL MCCLAIN, DANIEL RETA, JON G. C. KRAGSKOW, DAVID A. MARCHIORI, ELLA LACHMAN, XEUN-SANG CHOI, JAMES G. ANALYTIS, R. DAVID BRITT, NICHOLAS F. CHILTON, BENJAMIN G. HARVEY, JEFFREY R. LONG, Ultrahard magnetism from mixed-valence dilanthanide complexes with metal-metal bonding, SCIENCE 375, 198-202 (2022)

Hierarchical Assembly of Coordination Macromolecules with Atypical Geometries: Gd 44 Co 28 Crown and Gd 95 Co 60 Cage The discovered giant clusters are always highly symmetric owing to the spontaneous assembly of one or two basic units. The authors report the Gd 44 Co 28 crown and Gd 95 Co 60 cage, formulated as [Gd 44 Co 28 (IDA) 20 (OH) 72 (CO 3 ) 12 (OAc) 28 (H 2 O) 64 ]⋅(ClO 4 ) 24 and [Na 4 Gd 95 Co 60 (IDA) 40 (OH) 150 (CO 3 ) 40 (OAc) 58 (H 2 O) 164 ] ⋅ (ClO 4 ) 41 (H 2 IDA=iminodiacetic acid), respectively, by providing a library containing multiple low-nuclearity units. The heart-like units and crown-like tetramer found in both compounds indicate unprecedented assembly levels, leading to an atypical geometry characteristic compared to the giant clusters directly assembled by regular units. These two clusters not only significantly increase the size of Ln−Co clusters but also exhibit the enhanced magnetic entropy change at ultra-low temperatures. This work provided an effective way to fabricate cluster compounds with giant size and geometry complexity simultaneously. Ming-Hao Du, Dong-Hui Wang, Ling-Wei Wu, Lin-Peng Jiang, Jun-Ping Li, La-Sheng Long, Lan-Sun Zheng, Xiang-Jian Kong, Hierarchical Assembly of Coordination Macromolecules with Atypical Geometries: Gd 44 Co 28 Crown and Gd 95 Co 60 Cage, Angew. Chem. Int. Ed. (2022) in print

High-Performance Luminescence Thermometer with Field-Induced Slow Magnetic Relaxation Based on a Heterometallic Cyanido- Bridged 3d−4f Complex The 1:1:1 reaction of DyCl 3 ·6H 2 O, K 3 [Co(CN) 6 ] and bpyO 2 in H 2 O has provided access to a complex with formula [DyCo(CN) 6 (bpyO 2 ) 2 (H 2 O) 3 ]·4H 2 O ( 1 ) in a very good yield, while [DyFe(CN) 6 (bpyO 2 ) 2 (H 2 O) 3 ]·4H 2 O ( 2 ) was also precipitated (also in a high yield) using K 3 [Fe(CN) 6 ] instead of K 3 [Co(CN) 6 ]. Their structures have been determined by single-crystal X-ray crystallography and characterized based on elemental analyses and IR spectra. Combined direct current (dc) and alternating current (ac) magnetic susceptibility revealed slow magnetic relaxation upon application of a dc field. μ-SQUID measurements and CASSCF calculations revealed high-temperature relaxation dynamics for both compounds. Low-temperature magnetic studies show the relaxation characteristics for 1 , while for compound 2 the dynamics corresponds to an antiferromagnetically coupled Dy···Fe pair. High-resolution optical studies have been carried out to investigate the performance of compounds 1 and 2 as luminescence thermometers. For 1 , a maximum thermal sensitivity of 1.84% K –1 at 70 K has been calculated, which is higher than the acceptable sensitivity boundary of 1% K –1 for high-performance luminescence thermometers in a broad range of temperature between 40 and 140 K. Further optical studies focused on the chromaticity diagram of compound 1 revealed a temperature shift from warm white (3200 K) at 10 K toward a more natural white color near 4000 K at room temperature. Vassilis Tangoulis, Vassilis Nastopoulos, Nikos Panagiotou, Anastasios Tasiopoulos, Grigorios Itskos, Modestos Athanasiou, Eufemio Moreno-Pineda, Wolfgang Wernsdorfer, Michael Schulze, Ondrej Malina, High-Performance Luminescence Thermometer with Field-Induced Slow Magnetic Relaxation Based on a Heterometallic Cyanido- Bridged 3d−4f Complex, Inorg. Chem. (2022) in print

Implementation of Quantum Level Addressability and Geometric Phase Manipulation in Aligned Endohedral Fullerene Qudits Endohedral nitrogen fullerenes have been proposed as building blocks for quantum information processing due to their long spin coherence time. However, addressability of the individual electron spin levels in such a multiplet system of 4S3/2 has never been achieved because of the molecular isotropy and transition degeneracy among the Zeeman levels. Herein, by molecular engineering, the authors lifted the degeneracy by zero-field splitting effects and made the multiple transitions addressable by a liquid-crystal-assisted method. The endohedral nitrogen fullerene derivatives with rigid addends of spiro structure and large aspect ratios of regioselective bis-addition improve the ordering of the spin ensemble. These samples empower endohedral-fullerene-based qudits, in which the transitions between the 4 electron spin levels were respectively addressed and coherently manipulated. The quantum geometric phase manipulation, which has long been proposed for the advantages in error tolerance and gating speed, was implemented in a pure electron spin system using molecules for the first time. Dr. Shen Zhou, Jiayue Yuan, Zi-Yu Wang, Kun Ling, Peng-Xiang Fu, Yu-Hui Fang, Dr. Ye-Xin Wang, Dr. Zheng Liu, Prof. Kyriakos Porfyrakis, Prof. G. Andrew D. Briggs, Prof. Song Gao, Prof. Shang-Da Jiang, Implementation of Quantum Level Addressability and Geometric Phase Manipulation in Aligned Endohedral Fullerene Qudits, Angew. Chem. Int. Ed. (2021) early view

Heterospin frustration in a metal-fullerene-bonded semiconductive antiferromagnet Lithium-ion-encapsulated fullerenes (Li+@C60) are 3D superatoms with rich oxidative states. Here the authors show a conductive and magnetically frustrated metal–fullerene-bonded framework {[Cu4(Li@C60)(L)(py)4](NTf2)(hexane)}n (1) (L = 1,2,4,5-tetrakis(methanesulfonamido)benzene, py = pyridine, NTf2− = bis(trifluoromethane)sulfonamide anion) prepared from redox-active dinuclear metal complex Cu2(L)(py)4 and lithium-ion-encapsulated fullerene salt (Li+@C60)(NTf2−). Electron donor Cu2(L)(py)2 bonds to acceptor Li+@C60 via eight Cu‒C bonds. Cu–C bond formation stems from spontaneous charge transfer (CT) between Cu2(L)(py)4 and (Li+@C60)(NTf2−) by removing the two-terminal py molecules, yielding triplet ground state [Cu2(L)(py)2]+(Li+@C60•−), evidenced by absorption and electron paramagnetic resonance (EPR) spectra, magnetic properties and quantum chemical calculations. Moreover, Li+@C60•− radicals (S = ½) and Cu2+ ions (S = ½) interact antiferromagnetically in triangular spin lattices in the absence of long-range magnetic ordering to 1.8 K. The low-temperature heat capacity indicated that compound 1 is a potential candidate for an S = ½ quantum spin liquid (QSL). Yongbing Shen, Mengxing Cui, Shinya Takaishi, Hideyuki Kawasoko, Kunihisa Sugimoto, Takao Tsumuraya, Akihiro Otsuka, Eunsang Kwon, Takefumi Yoshida, Norihisa Hoshino, Kazuhiko Kawachi, Yasuhiko Kasama, Tomoyuki Akutagawa, Tomoteru Fukumura, Masahiro Yamashita, Heterospin frustration in a metal-fullerene-bonded semiconductive antiferromagnet, Nature Communications volume 13, Article number: 495 (2022)

Iron oxides at large scales Dissolution of FeBr3 in a mixture of acetonitrile and 3,4-lutidine in the presence of an amine results in the formation of an [Fe30] molecular metal oxide containing alternating layers of tetrahedral and octahedral FeIII ions. Mass spectrometry suggests the cluster is formed quickly and remains stable in solution, while magnetic measurements and DFT calculations reveal competing antiferromagnetic exchange interactions. Alice E. Dearle, Daniel J. Cutler, Marco Coletta, Edward Lee, Sourav Dey, Sergio Sanz, Hector W. L. Fraser, Gary S. Nichol, Gopalan Rajaraman, Jürgen Schnack, Leroy Cronin, Euan K. Brechin, An [FeIII30] molecular metal oxide, Chem. Commun., 2022,58, 52-55

A rare earth metallocene containing a 2,2′-azopyridyl radical anion Introducing spin onto organic ligands that are coordinated to rare earth metal ions allows direct exchange with metal spin centres. This is particularly relevant for the deeply buried 4f-orbitals of the lanthanide ions that can give rise to unparalleled magnetic properties. For efficacy of exchange coupling, the donor atoms of the radical ligand require high-spin density. Such molecules are extremely rare owing to their reactive nature that renders isolation and purification difficult. Here, we demonstrate that a 2,2′-azopyridyl (abpy) radical (S = 1/2) bound to the rare earth metal yttrium can be realized. This molecule represents the first rare earth metal complex containing an abpy radical and is unambigously characterized by X-ray crystallography, NMR, UV-Vis-NIR, and IR spectroscopy. In addition, the most stable isotope 89Y with a natural abundance of 100% and a nuclear spin of ½ allows an in-depth analysis of the yttrium–radical complex via EPR and HYSCORE spectroscopy. Further insight into the electronic ground state of the radical azobispyridine-coordinated metal complex was realized through unrestricted DFT calculations, which suggests that the unpaired spin density of the SOMO is heavily localized on the azo and pyridyl nitrogen atoms. The experimental results are supported by NBO calculations and give a comprehensive picture of the spin density of the azopyridyl ancillary ligand. This unexplored azopyridyl radical anion in heavy element chemistry bears crucial implications for the design of molecule-based magnets particularly comprising anisotropic lanthanide ions. Francis Delano IV, Ernesto Castellanos, John McCracken, Selvan Demir, A rare earth metallocene containing a 2,2′-azopyridyl radical anion, Chem. Sci., 2021,12, 15219-15228

Organometallic lanthanide bismuth cluster single-molecule magnets Single-molecule magnets (SMMs) are molecules that can retain magnetic polarization in the absence of an external magnetic field and embody the ultimate size limit for spin-based information storage and processing. Multimetallic lanthanide complexes lacking magnetic exchange coupling enable fast relaxation pathways that attenuate the full potential of these species. Employment of diamagnetic heavy main group elements with diffuse orbitals may lead to unprecedented strong coupling. Herein, two bismuth-cluster-bridged lanthanide complexes, [K(THF)4]2[Cp∗2Ln2Bi6] (Cp∗ = pentamethylcyclopentadienyl; 1-Ln, Ln = Tb, Dy), were synthesized via a solution organometallic approach. The neutral [Ln2Bi6] heterometallocubane core features lanthanide centers that are bridged by a rare Bi66− Zintl ion, which supports strong ferromagnetic interactions between lanthanides. This affords the rare observation of magnetic blocking and open hysteresis loops for superexchange-coupled SMMs comprising solely lanthanide ions. Both compounds constitute the first SMMs containing bismuth donors paving the way for promising synthetic targets for quantum computation. Peng Zhang, Florian Benner, Nicholas F. Chilton, Selvan Demir, Organometallic lanthanide bismuth cluster single-molecule magnets, Chem (2021)

Electronic control of strong magnetic anisotropy in Co-based single-molecule magnets The observation of large swings in the magnetic anisotropy in ligated Co2 dimers has motivated further calculations on single-center Co qubits in quasitetrahedral and quasioctahedral symmetries. In all cases results of the authors indicate that it is the creation of an unquenched orbital moment due to a half-occupied frontier state at the Co center that directly drives large changes in the magnetic anisotropy barriers regardless of whether it is through symmetry breaking, a change in the charge state, or orbital energy reordering. While these observations are computationally demonstrated through the results on both monomers and dimers, the origin of orbital reordering at the Fermi level is not describable in terms of single physical changes. For example, in ligated Co2 the appearance of an unquenched orbital moment in one of the Co centers is correlated with a change from antiferromagnetic to ferromagnetic ordering at an energy that is uncharacteristically high for such transitions. Because this raises the spector of electromagnetically switchable quantum devices that operate at higher temperatures relative to that of the first-generation magnetic qubits, the authors carefully discuss subtle details associated with single-center qubits in realistic atomistic environments. Zahra Hooshmand, Jie-Xiang Yu, Hai-Ping Cheng, and Mark R. Pederson, Electronic control of strong magnetic anisotropy in Co-based single-molecule magnets, Phys. Rev. B 104, 134411 (2021)

Generalized Heisenberg-Type Magnetic Phenomena in Coordination Polymers with Nickel-Lanthanide Dinuclear Units A new family of 3d-4f coordination polymers with the molecular formula [NiIILnIII(L)(dca)2(NO3)]n [Ln = Eu (1), Gd (2), Tb (3), Dy (4), and Ho (5); H2L = N,N′-bis(2-hydroxy-3-methoxy-5-methylbenzyl)homopiperazine; dca = dicyanamide] has been synthesized in search for new single-molecule magnet (SMM) materials containing highly anisotropic lanthanides. The magnetic properties of these materials have been established by DC and AC magnetometry and explained quantitatively by comprehensive phenomenological modeling based on a generalized Heisenberg-type model, hypothesized previously based on first-principles calculations. Single-crystal X-ray diffraction has shown that the compounds are isostructural, with lanthanide atoms occupying a nine-coordination site with muffin-like geometry and individual NiII–LnIII units linked by dca anions. Other than the paramagnetic compound 1, 2–5 exhibit intra-unit ferromagnetic 3d–4f interactions, favorable for a large spin ground state. A slow field-induced relaxation of magnetization has been observed in compound 4 (only), displaying a substantial energy barrier of Ueff/kB = 26.2(5) K, below 6 K. This is attributed to an easy-plane anisotropy and is consistent with the relaxation in systems with a Kramers ground state doublet and hyperfine interactions. Michał Antkowiak, Mithun Chandra Majee, Manoranjan Maity, Dhrubajyoti Mondal, Michalina Kaj, Monika Lesiów, Alina Bieńko, Leeor Kronik, Muktimoy Chaudhury, and Grzegorz Kamieniarz, Generalized Heisenberg-Type Magnetic Phenomena in Coordination Polymers with Nickel–Lanthanide Dinuclear Units, J. Phys. Chem. C 2021, 125, 20, 11182–11196

Inorganic Approach to Stabilizing Nanoscale Toroidicity in a Tetraicosanuclear Fe18Dy6 Single Molecule Magnet Cyclic coordination clusters (CCCs) are proving to provide an extra dimension in terms of exotic magnetic behavior as a result of their finite but cyclized chain structures. The Fe18Dy6 CCC is a Single Molecule Magnet with the highest nuclearity among Ln containing clusters. The three isostructural compounds [Fe18Ln6(μ-OH)6(ampd)12(Hampd)12(PhCO2)24](NO3)6·38MeCN for Ln = DyIII (1), LuIII (2), or YIII (3), where H2ampd = 2-amino-2-methyl-1,3-propanediol, are reported. These can be described in terms of the cyclization of six {Fe3Ln(μOH)(ampd)2(Hampd)2(PhCO2)4}+ units with six nitrate counterions to give the neutral cluster. The overall structure consists of two giant Dy3 triangles sandwiching a strongly antiferromagnetically coupled Fe18 ring, leading to a toroidal arrangement of the anisotropy axis of the Dy ions, making this the biggest toroidal arrangement on a molecular level known so far. Hagen Kaemmerer, Amer Baniodeh, Yan Peng, Eufemio Moreno-Pineda, Michael Schulze, Christopher E. Anson, Wolfgang Wernsdorfer, Jürgen Schnack, and Annie K. Powell, Inorganic Approach to Stabilizing Nanoscale Toroidicity in a Tetraicosanuclear Fe18Dy6 Single Molecule Magnet, J. Am. Chem. Soc. 142 (2020) 14838

Cooperative Effects in Heterometallic Complexes This special issue on “Cooperative effects in heterometallic complexes� documents research focused on the synthesis, physicochemical characterization, and theoretical description of ligand-stabilized homo- and heterobimetallic complexes containing only a few metal atoms – typically three. The authors call them 3MET complexes in short - also to reflect the title of the transregional collaborative research center 3MET.de founded in 2009 and located at the TU Kaiserslautern (TUK) and at the Karlsruhe Institute of Technology (KIT). Both fully coordinated and coordinatively unsaturatedspecies are of interest. In such 3MET complexes, the metalcenters are often bound by way of bridging ligands, whichfacilitate controlled variation of metal-to-metal distances andrelative orientations in order to characterize the correspondingstructure/property relations at a fundamental level. This in turnallows us to elucidate how metal–metal interactions in multi-nuclear complexes and clusters comprising transition-metaland/or lanthanide atoms contribute to determining theirproperties. It also enables the identification of optimal systemsand properties for future applications in the contexts ofphotoactive materials, optoelectronics, magnetic informationstorage, quantum computing, and selective catalysis. The 3MET consortium classifies cooperative effects accord-ing to three overall categories: 1) Functional cooperativity: Metal atom A and metal atom B comprise individual function-alities. The complex AB combines these and enables a novelfunctionality. 2) Enthalpic cooperativity: typically three metalcenters interacting with a substrate may together significantlychange the pathway of a rearrangement and thereby reduce itsoverall activation barrier. This constitutes enthalpic cooperativ-ity if the joint decrease of the barrier is larger than that due tothe separate metal centers. More generally, three bodyenthalpic cooperativity is present if the total enthalpy of thethree-body system is determined by more than pairwisecontributions of its components. 3) Entropic cooperativity: inbiochemistry, this effect is known as allosteric interaction: pre-orientation of a substrate (by active centers A and B) facilitatesits activation (by a third center C). Such effects are also of relevance, e.g., on surfaces in the case of deposited complexes. Special Issue: Cooperative Effects in Heterometallic Complexes, Chemistry - A European Journal, Volume 27, Issue 61 (2021) Pages: 15014-15271

High nuclearity polyoxometalates The syntheses and structures of a family of five new Ln/3d cluster containing polyoxometalates (POMs) [{(GeW9O34)2LnIII3(CO3)(OH2)3}6 {3MII2LnIII3(μ3-OH)6(OH2)6}4]50− {Ln30M8}, where Ln = Gd or Y, and M = Zn, Mn, Co, are presented. This structural motif of a giant tetrahedron contains {LnIII3} and {MII2LnIII3}-cluster units which are well-isolated within the diamagnetic polyoxotungstate system. The magnetic properties of {Gd30Mn8}, {Y30Mn8} and {Gd30Zn8} can be successfully modeled using a Heisenberg approach. Investigation of their magnetocaloric effect (MCE) reveals that this can be tuned through variation of the 3d metal ion. This is the first such systematic study on heterometallic 3d-4f- POM clusters. The {Gd30Zn8} analogue illustrates a promising way forward to magnetic cooling at sub-Kelvin temperatures. Masooma Ibrahim, Yan Peng, Eufemio Moreno-Pineda, Christopher E. Anson, Jürgen Schnack, Annie K. Powell, Gd3 Triangles in a Polyoxometalate Matrix: Tuning Molecular Magnetocaloric Effects in {Gd30M88} Polyoxometalate/Cluster Hybrids Through Variation of M2+, small structures, Volume2, Issue10, October 2021, 2100052 The 36-NiII-containing 54-tungsto-6-silicate, [Ni36(OH)18(H2O)36(SiW9O34)6]6− (Ni36) was discovered and shown to contain more nickel centers than any other polyoxometalate (POMs) known to date. Polyanion Ni36 comprises six equivalent {NiII6SiW9} units which are linked by Ni−O−W bridges forming a macrocyclic assembly. Magnetic studies indicate antiferromagnetic communication between the six {Ni6} subunits. Electrochemical studies indicate that the first reduction is reversible and associated to the WVI/V couple while the second reduction is irreversible and associated to the NiII/0 couple. Joydeb Goura, Bassem S. Bassil, Xiang Ma, Ananthu Rajan, Eufemio Moreno-Pineda, Jürgen Schnack, Masooma Ibrahim, Annie K. Powell, Mario Ruben, Jingjing Wang, Laurent Ruhlmann, Ulrich Kortz, NiII36-Containing 54-Tungsto-6-Silicate: Synthesis, Structure, Magnetic and Electrochemical Studies, Chemistry - A European Journal (2021) Early view Degradation of multilacunary precursors and the structure-directing effect of trilacunary Keggin {B-α-PW9O34} fragments under hydrothermal conditions in the presence of nickel ions result in formation of the largest Ni-substituted poly(polyoxotungstate)s known to date, which contain 20–22 Ni centers. The picture shows the X-ray structure of Ni22-substituted polyanion [H6Ni22X4W34(OH)4O136(H2O)6-(enMe)10]4− (enMe=1,2-diaminopropane). Xin-Xiong Li, Shou-Tian Zheng, Jie Zhang, Wei-Hui Fang, Guo-Yu Yang, Juan Modesto Clemente-Juan, High-Nuclearity Ni-Substituted Polyoxometalates: A Series of Poly(polyoxotungstate)s Containing 20–22 Nickel Centers, Chemistry - A European Journal (2021) Early view

Magnetic anisotropies of Ho(iii) and Dy(iii) single-molecule magnets experimentally determined via polarized neutron diffraction The authors present the magnetic anisotropy of two isostructural pentagonal-bipyramidal complexes, [Ln(H2O)5(HMPA)2]I3·2HMPA (HMPA = hexamethylphosphoramide, Ln = Dy, Ho). Using ac magnetic susceptibility measurements, we find magnetic relaxation barriers of 600 K and 270 K for the Dy- and Ho-compounds, respectively. This difference is supported by polarized neutron diffraction (PND) measured at 5 K and 1 T which provides the first experimental evidence that the transverse elements in the magnetic anisotropy of the Ho-analogue are significant, whereas the Dy-analogue has a near-axial magnetic anisotropy with vanishing transverse contributions. The coordination geometries of the two complexes are highly similar, and we attribute the loss of strong magnetic axiality as expressed in the atomic susceptibility tensors from PND, as well as the smaller relaxation barrier in the Ho-complex compared to the Dy-complex, to the less favorable interaction of the pentagonal bipyramidal crystal field with the characteristics of the Ho(III) 4f-charge distribution. Emil A. Klahn, Andreas M. Thiel, Rasmus B. Degn, Iurii Kibalin, Arsen Gukassov, Claire Wilson, Angelos B. Canaj, Mark Murrie, Jacob Overgaard, Magnetic anisotropies of Ho(iii) and Dy(iii) single-molecule magnets experimentally determined via polarized neutron diffraction, Dalton Trans., 2021, Advance Article

A dissymmetric [Gd2] coordination molecular dimer hosting six addressable spin qubits Artificial magnetic molecules can host several spin qubits, which could then implement small-scale algorithms. In order to become of practical use, such molecular spin processors need to increase the available computational space and warrant universal operations. Here, the authors design, synthesize and fully characterize dissymetric molecular dimers hosting either one or two Gadolinium(III) ions. The strong sensitivity of Gadolinium magnetic anisotropy to its local coordination gives rise to different zero-field splittings at each metal site. As a result, the [LaGd] and [GdLu] complexes provide realizations of distinct spin qudits with eight unequally spaced levels. In the [Gd2] dimer, these properties are combined with a Gd-Gd magnetic interaction, sufficiently strong to lift all level degeneracies, yet sufficiently weak to keep all levels within an experimentally accessible energy window. The spin Hamiltonian of this dimer allows a complete set of operations to act as a 64-dimensional all-electron spin qudit, or, equivalently, as six addressable qubits. Electron paramagnetic resonance experiments show that resonant transitions between different spin states can be coherently controlled, with coherence times TM of the order of 1 microsecond limited by hyperfine interactions. Coordination complexes with embedded quantum functionalities are promising building blocks for quantum computation and simulation hybrid platforms. Fernando Luis, Pablo J. Alonso, Olivier Roubeau, Verónica Velasco, David Zueco, David Aguilà, Jesús I. Martínez, Leoní A. Barrios, Guillem Aromí, A dissymmetric [Gd2] coordination molecular dimer hosting six addressable spin qubits, Commun Chem 3, 176 (2020)

Measuring molecular magnets for quantum technologies Single-molecule magnets (SMMs) have been proposed for applications in high-density storage, quantum simulation, quantum computing and spintronics applications. Bulk magnetometric and spectroscopic techniques of molecular systems have allowed the observation of remarkable quantum effects in SMMs, such as the observation of an energy barrier, the reversal of the magnetization and quantum tunnelling of the magnetization. Over the past 10 years, scanning tunnelling microscopy of SMMs and single-molecule devices architectures, such as spin valves and spin transistors, have shed light onto the quantum properties of SMMs at the single-molecule level. More recently, new techniques, where the spin degrees of freedom in SMMs can be read out by photons, are being studied. Here, the authors review key techniques allowing the observation of quantum effects, important for the initialization, control and readout of the states of the SMMs, ultimately leading to the implementation of SMMs in technological applications. Eufemio Moreno-Pineda, Wolfgang Wernsdorfer, Measuring molecular magnets for quantum technologies, Nat. Rev. Phys. (2021)

Principal component analysis of diffuse magnetic neutron scattering: a theoretical study The authors present a theoretical study of the potential of principal component (PC) analysis to analyse magnetic diffuse neutron scattering data on quantum materials. To address this question, the authors simulate the scattering function S(q) for a model describing a cluster magnet with anisotropic spin–spin interactions under different conditions of applied field and temperature. The authors find high dimensionality reduction and that the algorithm can be trained with surprisingly small numbers of simulated observations. Subsequently, observations can be projected onto the reduced-dimensionality space defined by the learnt PCs. Constant-field temperature scans correspond to trajectories in this space which show characteristic bifurcations at the critical fields corresponding to ground-state phase boundaries. Such plots allow the ground-state phase diagram to be accurately determined from finite-temperature measurements. Robert Twyman, Stuart J. Gibson, James Molony, Jorge Quintanilla, Principal component analysis of diffuse magnetic neutron scattering: a theoretical study, J. Phys.: Condens. Matter 33, 324002 (2021)

Point-group selection rules and universal momentum-transfer dependencies for inelastic neutron scattering on molecular spin clusters Recent significant progress in inelastic neutron scattering (INS) has rendered this technique even more useful for the characterization of magnetic systems, including molecular spin clusters. By so-called four-dimensional INS on single-crystal probes, excitation spectra can be recorded in large portions of momentum-transfer (Q) and energy-transfer (E) space. Spin-selection rules permit certain transitions between different spin multiplets. Additional selection rules can be imposed by point-group symmetry but were not discussed yet. As most synthetic spin clusters with interesting magnetic properties have high molecular symmetry, a clear understanding of this issue will be helpful for interpreting INS spectra. Here the author discusses point-group INS selection rules for magnetically isotropic or anisotropic spin clusters. Rings and a number of spin polyhedra with cubic or icosahedral symmetry are chosen as illustrative and relevant examples. These systems exhibit a significant number of point-group selection rules in isotropic spin models, and most of them maintain a smaller number of selection rules in anisotropic spin models. The author also explains how the Q dependence of certain excitations depends exclusively on the point-group symmetry of the states involved in the transition, an aspect that had thus far only been detailed for spin rings. The author provides the universal Q-dependent intensity functions (and their powder-averaged forms) for a set of polyhedra (cube, icosahedron, truncated tetrahedron, cuboctahedron, dodecahedron, icosidodecahedron, and truncated icosahedron). Overall, these results help to disentangle the relevant dynamical information contained in INS spectra from those features that are entirely determined by molecular symmetry. Shadan Ghassemi Tabrizi, Point-group selection rules and universal momentum-transfer dependencies for inelastic neutron scattering on molecular spin clusters, Phys. Rev. B 103, 214422

Spectral Addressability in a Modular Two Qubit System Electron spins in molecular transition metal complexes are a highly tunable platform for the creation of quantum bits (qubits) from the bottom-up. To leverage this control in systems of multiple qubits, we need to be able to address each qubit independently and understand their impact on one another as a function of their spatial relationship. To this end, we designed and synthesized a series of molecules bearing two spectrally-resolved qubits, a d1 Ti3+ and a d9 Cu2+ center, in a rigid ligand framework that enforces 1.2-2.5 nm distances between them. Through a combination of pulse EPR spectroscopy, control of matrix effects, and comparison to the monometallic analogues, we disentangle the many contributions to decoherence of the qubit state. Despite their magnetic interactions, the proximity of a second qubit's electron spin does not limit coherence of the first due to commensurate relaxation rates and different resonance frequencies. Quantum state tomography, however, can detect the impact of the second qubit on the coherent evolution of the qubit's quantum state. These findings point to the power of chemical synthesis to create complex designer quantum systems and will guide future development of multifunctional systems of many qubits. von Kugelgen, S.; Krzyaniak, M. D.; Gu, M.; Puggioni, D.; Rondinelli, J. M.; Wasielewski, M. R.; Freedman, D. E., Spectral Addressability in a Modular Two Qubit System, J. Am. Chem. Soc. 2021, 143 (21), 8069–8077

Optically addressable molecular spins for quantum information processing Molecular spins provide a chemically tunable platform to design quantum bits (qubits) from the bottom up. However, molecular qubits typically lack mechanisms to optically control the ground state spin, which would be a transformative capability for this modular and scalable class of qubits. In this work, we design spin-triplet molecular systems where the electronic structure enables optical initialization and readout of the ground state spin, similar to optically addressable defect-based systems. In doing so, we target pseudo tetrahedral CrR4, where R is an aryl-type ligand. The pseudo-tetrahedral aryl ligand field minimizes the ground state zero-field splitting in these d2, Cr4+ compounds. Additionally, the strong-field aryl donors generate the desired excited state structure where the first excited state is a spin-singlet. With this cumulative electronic structure, we demonstrate optical spin initialization and readout, as well as coherent spin manipulation with each Cr4+ compound. Moreover, we highlight that minor ligand modifications modulate the resulting spin and optical properties. Our results illustrate that these synthetically flexible Cr4+ systems offer a platform to realize designer optically addressable molecular spins for quantum technologies. Bayliss, S. L.; Laorenza, D. W.; Mintun, P. J.; Kovos, B. D.; Freedman, D. E.; Awschalom, D. D., Optically addressable molecular spins for quantum information processing, Science, 2020, 370, 1309-1312

The Limit of Spin Lifetime in Solid-State Electronic Spins Achieving a full chemical control of spin lifetime is a central challenge in molecular magnetism, as it determines our ability to manipulate spin for technological applications. However, the success in this area is hindered but the lack of understanding of the details of spin-lattice relaxation. One of the biggest obstacles in the field is represented by the phenomenological nature of current spin relaxation theories, which were derived under strong approximations and for solid-state impurities. In this contribution, the authors completed the development of a fully-ab initio computational strategy, inclusive of both direct and Raman relaxation mechanisms, to predict spin-lattice relaxation time in S=1/2 systems. The method is parameter-free and is based on a combination of periodic-density functional theory calculations, used to determine lattice vibrations, and wave-function theory, which is used to determine all the spin-lattice coupling coefficients. Moreover, a machine-learning strategy is presented as a mean to speed up simulations of orders of magnitude, making simulations feasible for realistic systems. Results show that the direct mechanism drives relaxation at low-temperature and at very high fields, while at high-temperature Raman mechanism is the main responsible for relaxation. A physically inspired formula for the fitting of relaxation time as a function of temperature is proposed and used to provide a robust interpretation of experimental results. Importantly, it is shown that phonons in the THz frequency window are responsible for relaxation at high-temperature, offering a new rationale for the chemical control of relaxation time. A. Lunghi, S. Sanvito, The Limit of Spin Lifetime in Solid-State Electronic Spins, Journal of Physical Chemistry Letters 11 (15), 6273-6278, 2020

Substantial π-aromaticity in the anionic heavy-metal cluster [Th@Bi12]4− The concept of aromaticity was originally defined as a property of unsaturated, cyclic planar organic molecules like benzene, which gain stability by the inherent delocalization of 4n + 2 π-electrons over the ring atoms. Since then, π-aromaticity has been observed for a large variety of organic and inorganic non-metal compounds, yet, for molecules consisting only of metal atoms, it has remained restricted to systems with three to five atoms. Here, the authors present the straightforward synthesis of a metal 12-ring that exhibits 2π-aromaticity and has a ring current much stronger than that of benzene (6π) and equivalent to that of porphine (26π), despite these organic molecules having (much) larger numbers of π-electrons. Highly reducing reaction conditions allowed access to the heterometallic anion [Th@Bi12]4−, with interstitial Th4+ stabilizing a Bi128− moiety. The results show that it is possible to design and generate substantial π-aromaticity in large metal rings, and the authors hope that such π-aromatic heavy-metal cycles will eventually find use in cluster-based reactions. Armin R. Eulenstein, Yannick J. Franzke, Niels Lichtenberger, Robert J. Wilson, H. Lars Deubner, Florian Kraus, Rodolphe Clérac, Florian Weigend, Stefanie Dehnen, Substantial π-aromaticity in the anionic heavy-metal cluster [Th@Bi12]4−, Nature Chemistry volume 13, pages 149–155 (2021)

A reaction-coordinate perspective of magnetic relaxation Understanding and utilizing the dynamic quantum properties of metal ions is the frontier of many next generation technologies. One property in particular, magnetic relaxation, is a complicated physical phenomenon that is scarcely treated in undergraduate coursework. Consequently, principles of magnetic relaxation are nearly impenetrable to starting synthetic chemists, who ultimately design the molecules that fuel new discoveries. In this Tutorial Review, the authors describe a new paradigm for thinking of magnetic relaxation in metal complexes in terms of a simple reaction-coordinate diagram to facilitate access to the field. They cover the main mechanisms of both spin–lattice (T1) and spin–spin (T2) relaxation times within this conceptual framework and how molecular and environmental design affects these times. Ultimately, the authors show that many of the scientific methods used by inorganic chemists to study and manipulate reactivity are also useful for understanding and controlling magnetic relaxation. They also describe the cutting edge of magnetic relaxation within this paradigm. Cassidy E. Jackson, Ian P. Moseley, Roxanna Martinez, Siyoung Sung, Joseph M. Zadrozny, A reaction-coordinate perspective of magnetic relaxation, Chem. Soc. Rev., 2021, Advance Article

Single-Molecule Magnets: From Mn12-ac to dysprosium metallocenes, a travel in time The discovery of the first Single-Molecule Magnet, Mn12-ac, in 1993 changed the perspective of how information can be stored. The current bit, occupying few hundreds of nanometers in present devices, would be minimized to tens of angstroms at molecular level. However, until a couple of years these materials could only operate at temperatures near to the absolute zero. From 1993 to date, the field of Single-Molecule Magnets (SMMs) has continuously evolved thanks to the close collaboration of chemists and physicists obtaining materials already operating above the liquid nitrogen temperature. This long journey, however, has involved the study of many different routes towards high performance SMMs, being each of them essential in order to deeply understand the quantum dynamics behind these molecules. An era of high spin 3d metal clusters was the beginning of everything, but it went through highly anisotropic low coordinate 3d compounds, lanthanide based magnets, radical bridged compounds and 3d-4f mixed systems, among others, to end up in the current state of the art dysprosium metallocenes. Furthermore, after the magnetic studies in bulk, SMM based hybrid systems are emerging for future application devices, which also involve very interesting multifunctionalities. All in all, this work aims to explain how these materials work and show the trajectory and some of the major advances that have been made during recent years in this field. Andoni Zabala-Lekuona, Jose Manuel Seco, Enrique Colacio, Single-Molecule Magnets: From Mn12-ac to dysprosium metallocenes, a travel in time, Coordination Chemistry Reviews, Volume 441, 15 August 2021, 213984

Tuning the Ferrotoroidic Coupling and Magnetic Hysteresis in Double-Triangle Complexes {Dy3MIIIDy3} via the MIII-linker The authors present the syntheses, structures, magnetic data and theoretical analyses for two families of heptanuclear clusters, wherein two staggered dysprosium(III) triangles are linked by various M(III) d-/p-block ions. The families differ in the counter-anion and are of formulae [DyIII6MIII(OH)8(o-tol)12(MeOH)5(NO3)] ⋅ 4MeOH and [DyIII6MIII(OH)8(o-tol)12(MeOH)6]Cl ⋅ 6MeOH (M=Cr, Mn, Fe, Co, Al; o-tol=o-toluate). The authors find that variation of the central metal ion M is crucial in tuning the toroidal moments on the triangular units, with diamagnetic M linking ions enhancing the ferrotoroidic coupling. By detailed simulation and analysis of various magnetic measurements, including sub-kelvin microSquid hysteresis loops, the authors identified the specific signature of the M linking ions’ modulation of toroidal properties, including the mechanism whereby anisotropic, paramagnetic M ions lead to hysteresis profiles with larger remnant magnetisations and broader coercive fields. Jared M. Ashtree, Ivana Borilovic, Kuduva R. Vignesh, Abinash Swain, Sarah H. Hamilton, Yasmin L. Whyatt, Sophie L. Benjamin, Wasinee Phonsri, Craig M. Forsyth, Wolfgang Wernsdorfer, Alessandro Soncini, Gopalan Rajaraman, Stuart K. Langley, Keith S. Murray, Tuning the Ferrotoroidic Coupling and Magnetic Hysteresis in Double-Triangle Complexes {Dy3MIIIDy3} via the MIII-linker, Eur. J. Inorg. Chem., Volume 2021, Issue 5, February 5, 2021 Pages 435-444

A giant spin molecule with ninety-six parallel unpaired electrons Unpaired electrons which are essential for organic radicals and magnetic materials are hard to align parallel, especially with increasing of number of spins. Here, the authors show that the antiferromagnetic interaction in the largest Cr(III)-RE (rare earth) cluster {Cr10RE18} leads to 96 parallel electronic spins, forming a ground state spin of 48 for RE = Gd. This is so far the third largest ground state spin achieved in one molecule. Moreover, by using classical Monte Carlo simulations, the exchange coupling constants can be determined. Spin dynamics simulation reveals that the strong Zeeman effect of 18 Gd(III) ions stabilizes the ground ferrimagnetic state and hinder the magnetization reversal of these spins. In addition, the dysprosium(III) analog is an exchange-biasing single-molecule magnet. The authors believe that the ferrimagnetic approach and analytical protocol established in their work can be applied generally in constructing and analyzing giant spin molecules. LeiQin, Hao-LanZhang, Yuan-Qi Zhai, Hiroyuki Nojiri, Christian Schröder, Yan-Zhen Zheng, A giant spin molecule with ninety-six parallel unpaired electrons, iScience, Volume 24, Issue 4, 23 April 2021, 102350

In Quest of Molecular Materials for Quantum Cellular Automata: Exploration of the Double Exchange in the Two-Mode Vibronic Model of a Dimeric Mixed Valence Cell In this article, the authors apply the two-mode vibronic model to the study of the dimeric molecular mixed-valence cell for quantum cellular automata. As such, the authors consider a multielectron mixed valence binuclear d2−d1–type cluster, in which the double exchange, as well as the Heisenberg-Dirac-Van Vleck exchange interactions are operative, and also the local (breathing) and intercenter vibrational modes are taken into account. The calculations of spin-vibronic energy spectra and the cell-cell-response function are carried out using quantum-mechanical two-mode vibronic approach based on the numerical solution of the dynamic vibronic problem. The obtained results demonstrate a possibility of combining the function of molecular QCA with that of spin switching in one electronic device and are expected to be useful from the point of view of the rational design of such multifunctional molecular electronic devices. Boris Tsukerblat, Andrew Palii, Sergey Aldoshin, In Quest of Molecular Materials for Quantum Cellular Automata: Exploration of the Double Exchange in the Two-Mode Vibronic Model of a Dimeric Mixed Valence Cell, Magnetochemistry 2021, 7(5), 66 See Special Issue "Perspectives on Molecular Materials—A Tribute to Professor Peter Day", Magnetochemistry 2021

Mixed-valence clusters: Prospects for single-molecule magnetoelectrics In this review the authors summarize the results of recent studies of the mechanisms of magnetoelectric effect in mixed-valence molecules. Consideration of fairly different systems and emerging situations is united by a common physical concept of spin-dependent electric polarizability in a wide class of such systems. In many-electron dimers, which are on the borderline between the Robin and Day classes II and III, the electric field suppresses ferromagnetic double-exchange and induces electric dipole moment, while the antiferromagnetic Heisenberg-type exchange remains unaffected. This leads to stabilization of the low-spin states thus giving rise to the spin-switching effect. A short and to a large extent qualitative discussion of the role of the vibronic coupling that is inherent for mixed valence systems is given as well. In trigonal trimers with two delocalized excess electrons, the electric field suppresses the first-order electron transfer, and under some conditions also leads to the spin-switching effect. Magnetoelectric coupling of quite different nature occurs in linear two-electron trimers (such as linear triferrocenium complexes) and also in two-electron clusters of higher complexity such as polyoxoanion [GeV14O40]8−. In these systems electric field is shown to effectively approach the two remote electrons, thus forcing them to interact. This allows to enable/disable the exchange interaction by turning on/off the electric field. We also discuss a possibility to control spin-states in the two-electron square-planar systems acting as cells in molecular quantum cellular automata devices. Spin-singlets and spin-triplets exhibit different electric polarizabilities, which allows to control the spin-states by using polarized driver-cell. Finally, the authors briefly discuss the feasibility of the electric field control of mixed valence molecules and also give some additional examples of clusters exhibiting magnetoelectrical effect. Andrew Palii, Sergey Aldoshin, Boris Tsukerblat, Mixed-valence clusters: Prospects for single-molecule magnetoelectrics, Coordination Chemistry Reviews, Volume 426, 1 January 2021, 213555

Mononuclear Dysprosium Alkoxide and Aryloxide Single�Molecule Magnets Recent studies have shown that mononuclear lanthanide (Ln) complexes can be high�performing single�molecule magnets (SMMs). Recently, there has been an influx of mononuclear Ln alkoxide and aryloxide SMMs, which have provided the necessary geometrical control to improve SMM properties and to allow the intricate relaxation dynamics of Ln SMMs to be studied in detail. Here non�aqueous Ln alkoxide and aryloxide chemistry applied to the synthesis of low�coordinate mononuclear Ln SMMs are reviewed. The focus is on mononuclear DyIII alkoxide and aryloxide SMMs with coordination numbers up to eight, covering synthesis, solid�state structures and magnetic attributes. Brief overviews are also provided of mononuclear TbIII, HoIII, ErIII and YbIII alkoxide and aryloxide SMMs. Vijay S. Parmar, David P. Mills, Richard E. P. Winpenny, Mononuclear Dysprosium Alkoxide and Aryloxide Single�Molecule Magnets, Chem. Eur. J. (2021) Early view

The Synthesis and Characterisation of a Molecular Seaâ€�Serpent: Studies of a {Cr24Cu7} Chain A finite chain of thirtyâ€�one paramagnetic centers is reported, synthesized by reaction of hydrated chromium fluoride, copper carbonate and pivalic acid in the presence of 1,4,7,10â€�tetrazacyclododecane (cyclen). Magnetic studies show predominantly antiâ€�ferromagnetic exchange leading to a high density of lowâ€�lying spin states and large saturation field. Rajeh Alotaibi, Jonathan M. Fowler, Selena J. Lockyer, Grigore A. Timco, David Collison, Jürgen Schnack, Richard E. P. Winpenny, The Synthesis and Characterisation of a Molecular Seaâ€�Serpent: Studies of a {Cr24Cu7} Chain, Angew. Chem. Int. Ed. 60 (2021) 9489

Strong Coupling and Slow Relaxation of the Magnetization for an Air-Stable [Co4] Square with Both Tetrazine Radicals and Azido Bridges Derivatives of 3,6-substituted tetrazine with parallel coordination sites have served as promising coding ligands for the most common motif of square structures and their anion radical forms have proved to be capable of transmitting robust magnetic interactions. In light of the pre-programmed ability and redox-activity of these ligands, herein we report the synthesis, structures and magnetic studies of the azido-bpztz co-bridged molecular squares [MII4(bpztz·-)4(N3)4] (MII = Zn2+, 1; Co2+, 2; bpztz = 3,6-bis(3,5-dimethyl-pyrazolyl)-1,2,4,5-tetrazine, TOC as below). Interestingly, the rare cis-bridging mode of tetrazine radicals dictated by the EO-azido bridges provided a pleasant molecular magnetic anisotropy for single molecule magnets and as a result, strong magnetic interactions between metal spin centers and the radicals (J = -64.7 cm-1) were realized in 2. Remarkably, high-performance single-molecule magnet behavior with an effective energy barrier of 92 K of 2 under a zero-dc field was observed, which is the first example of a cis-tetrazine radical bridged [Co4] square and among the highest relaxation barriers for reported polynuclear transition-metal compounds. Zhilin Guo, Yi-Fei Deng, Zoe Pikramenou, Kim R. Dunbar, and Yuan-Zhu Zhang, Strong Coupling and Slow Relaxation of the Magnetization for an Air-Stable [Co4] Square with Both Tetrazine Radicals and Azido Bridges, Inorg. Chem. 2021, in print

Complete mapping of the thermoelectric properties of a single molecule Theoretical studies suggest that mastering the thermocurrent through single molecules can lead to thermoelectric energy harvesters with unprecedentedly high efficiencies. This can be achieved by engineering molecule length, optimizing the tunnel coupling strength of molecules via chemical anchor groups or by creating localized states in the backbone with resulting quantum interference features. Empirical verification of these predictions, however, faces considerable experimental challenges and is still awaited. Here the authors use a novel measurement protocol that simultaneously probes the conductance and thermocurrent flow as a function of bias voltage and gate voltage. They find that the resulting thermocurrent is strongly asymmetric with respect to the gate voltage, with evidence of molecular excited states in the thermocurrent Coulomb diamond maps. These features can be reproduced by a rate-equation model only if it accounts for both the vibrational coupling and the electronic degeneracies, thus giving direct insight into the interplay of electronic and vibrational degrees of freedom, and the role of spin entropy in single molecules. Overall these results show that thermocurrent measurements can be used as a spectroscopic tool to access molecule-specific quantum transport phenomena. Pascal Gehring, Jakub K. Sowa, Chunwei Hsu, Joeri de Bruijckere, Martijn van der Star, Jennifer J. Le Roy, Lapo Bogani, Erik M. Gauger, Herre S. J. van der Zant, Complete mapping of the thermoelectric properties of a single molecule, Nat. Nanotechnol. (2021)

Next Generation Multifunctional Nano-Science of Advanced Metal Complexes with Quantum Effect and Nonlinearity The author's research target can be described as "Next Generation Multifunctional Nano-Science of Advanced Metal Complexes with Quantum Effect and Nonlinearity". His work encompasses four important key areas: (1) inorganic-organic hybrid systems, (2) nano-size and nano-space, (3) bottom-up and self-assembly, and (4) nonlinearity and quantum effect. Among them, nonlinearity and quantum effect are the most important for nano-science of advanced metal complexes. The author has been working on these two topics (nonlinearity and quantum effect) simultaneously for more than 40 years. As for quantum effect, he has focused on Haldane gap systems, single-chain magnets (SCMs), single-molecule magnets (SMMs), Kondo resonance on SMMs, photo-switchable SMMs, metallic conducting SMMs, SMMs encapsulated into single-walled carbon nanotube (SWCNT), and metal-organic framework (MOF)-spintronics for spin qubits, for pursuing high-density memory devices and quantum computing. As for nonlinearity, he has focused on quasi-one-dimensional halogen-bridged metal complexes (MX-Chains; M = Pt, Pd, and Ni; X = Cl, Br, and I) with nonlinear excitons such as solitons and polarons, strongly electron-correlated Ni(III) complexes with gigantic third-order optical nonlinearity, and phase transitions and charge fluctuations between Pd(III) averaged states (= Mott insulator) and Pd(II)-Pd(IV) mixed-valence states (= charge density wave states), for pursuing optical communication, optical switching, and optical computing. In this review article, the above main topics (quantum effect and nonlinearity) will be described according to the author's research history of more than 40 years, Future perspectives for the two topics will be proposed. Masahiro Yamashita, Next Generation Multifunctional Nano-Science of Advanced Metal Complexes with Quantum Effect and Nonlinearity, Bulletin of the Chemical Society of Japan, 2021, Vol.94, No.1

Quantum Phase Interference in the Excited Triplet of C70 High spin magnetic molecules are promising candidates for quantum information processing because their intrinsic multiplicity facilitates information storage and computational operations. However, due to the absence of suitable sublevel splittings, their susceptibility to environmental disturbances and limitation from the selection rule, the arbitrary control of the quantum state of a molecular electron multiplet has not been realized. Here Prof. ShangDa Jiang and Prof. Song Gao’s group exploited the photoexcited triplet of C70 as a molecular electron spin qutrit with pulsed electron paramagnetic resonance. They prepared the system into 3-level superposition states characteristic of a qutrit and validated them by the tomography of their density matrices. To further elucidate the coherence of the operation and the nature of the system as a qutrit, they demonstrated the quantum phase interference in the superposition. The interference pattern is further interpreted as a map of possible evolution paths in the space of phase factors, representing the quantum nature of the 3-level system. Ye-Xin Wang, Zheng Liu, Yu-Hui Fang, Shen Zhou, Shang-Da Jiang, Song Gao, Coherent manipulation and quantum phase interference in a fullerene-based electron triplet molecular qutrit, npj Quantum Inf 7, 32 (2021)

Spinâ€�Electric Coupling in a Cobalt(II)â€�Based Spin Triangle Revealed by Electric Fieldâ€�Modulated ESR The authors report on a cobalt(II)â€�based spin triangle showing a significant spinâ€�electric coupling. In analogy with a previously investigated modification, the intraâ€�triangle antiferromagnetic interaction leads to spin frustration. The two expected energy degenerate ground doublets are, however, separated by a few wavenumbers, as a consequence of magnetic anisotropy and deviations from threefold symmetry. At variance with the previously investigated modification, the Co3 planes of symmetryâ€�related molecules are almost parallel, allowing for the determination of the spinâ€�electric properties on single crystals by electric fieldâ€�modulated electron spin resonance spectroscopy (EFMâ€�ESR). The spinâ€�electric effect detected when the electric field is applied in the Co3 plane was revealed by a shift in the resonance field. Its value is comparable to what was determined for a Cu3 triangle despite the antiferromagnetic interaction being 20 times larger for the latter. Benjamin Kintzel, Maria Fittipaldi, Michael Böhme, Alberto Cini, Lorenzo Tesi, Axel Buchholz, Roberta Sessoli, Winfried Plass, Spinâ€�Electric Coupling in a Cobalt(II)â€�Based Spin Triangle Revealed by Electric Fieldâ€�Modulated ESR, Angew. Chem. Int. Ed. (2021) accepted

Direct spectroscopic observation of Berry-phase interference in the Ni4 single-molecule magnet Berry-phase effects in spin systems lead to the suppression of tunneling effects when different tunneling paths interfere destructively. Such effects have been seen in several single-molecule magnets (SMMs) through measurements of magnetization dynamics, where the experimental signal may arise from the contributions of numerous energy levels. Here the authors present experimental measurements of Berry-phase interference effects that are determined through electron-spin resonance on a fourfold symmetric SMM. Specifically, the authors measure transitions between tunnel-split excited states in the Ni4 SMM in the presence of a transverse field in the hard plane of the crystalline sample. By using a home-built rotation apparatus, the direction of the sample can be changed in situ so that the field direction can be swept through the entire hard plane of the sample. When the field is in certain directions in the plane, the authors observe a splitting of the transition, a hallmark of Berry-phase interference. The experimental results are well reproduced by numerical simulations, and fitting of the data provides information about the effects of dipolar interactions and sample misalignment. Brendan C. Sheehan, Robert Kwark, Charles A. Collett, Thomaz A. Costa, Rafael A. Allão Cassaro, and Jonathan R. Friedman, Direct spectroscopic observation of Berry-phase interference in the Ni4 single-molecule magnet, Phys. Rev. B 102, 224428 (2020)

Understanding magnetic relaxation in single-ion magnets with high blocking temperature The recent discovery of single-ion magnets with magnetic hysteresis above liquid-nitrogen temperatures placed these compounds among the best candidates to realize high-density storage devices. Starting from a prototypical dysprosocenium molecule, showing hysteresis up to 60 K, the authors derive here a general recipe to design high-blocking-temperature rare-earth single-ion magnets. The complex magnetic relaxation is unraveled by combining magnetization and nuclear magnetic resonance measurements with inelastic neutron scattering experiments and ab initio calculations, thus disentangling the different mechanisms and identifying the key ingredients behind slow relaxation. A. Chiesa, F. Cugini, R. Hussain, E. Macaluso, G. Allodi, E. Garlatti, M. Giansiracusa, C. A. P. Goodwin, F. Ortu, D. Reta, J. M. Skelton, T. Guidi, P. Santini, M. Solzi, R. De Renzi, D. P. Mills, N. F. Chilton, and S. Carretta, Understanding magnetic relaxation in single-ion magnets with high blocking temperature, Phys. Rev. B 101, 174402 (2020)

Blocking like it's hot: a synthetic chemists’ path to high-temperature lanthanide single molecule magnets Progress in the synthesis, design, and characterisation of single-molecule magnets (SMMs) has expanded dramatically from curiosity driven beginnings to molecules that retain magnetization above the boiling point of liquid nitrogen. This is in no small part due to the increasingly collaborative nature of this research where synthetic targets are guided by theoretical design criteria. This article aims to summarize these efforts and progress from the perspective of a synthetic chemist with a focus on how chemistry can modulate physical properties. A simple overview is presented of lanthanide electronic structure in order to contextualize the synthetic advances that have led to drastic improvements in the performance of lanthanide-based SMMs from the early 2000s to the late 2010s. Conrad A. P. Goodwin, Blocking like it's hot: a synthetic chemists’ path to high-temperature lanthanide single molecule magnets, Dalton Trans., 2020,49, 14320-14337

Secondary metal coordination using a tetranuclear complex as ligand leading to hexanuclear complexes with enhanced thermal barriers for electron transfer Post-synthesis of the paramagnetic square-shaped complex {[(Tp*Me)Fe(μ-CN)2(CN)][Co(dmbpy)2]}2(BPh4)2·6MeCN·H2O [ 1, Tp*Me = tris(3,4,5-trimethylpyrazole)-borate; dmbpy = 4,4′-dimethyl-2,2′-bipyridine)] by grafting transition metal(II) thiocyanates via its terminal cyano groups afforded three hexanuclear [Fe2Co2M2] clusters (M = Zn, 2; Co, 3; Cd, 4). The peripheral metal complex units serving as excellent electron acceptors were found to help stabilize the low-temperature state of FeII,LS-CoIII,LS within the complex core. As a result, the desolvated complexes 2 to 4 underwent reversible and sharp thermally induced electron-transfer behavior with the transition temperatures (T1/2) up to 312, 296 and 365 K, respectively, demonstrating an effective means of manipulating thermal barriers of the celebrated cyano-bridged square core. Shihao Liu, Yi-Fei Deng, Zi-Yi Chen, Lingyi Meng, Xiaoyong Chang, Zhiping Zheng, and Yuan-Zhu Zhang, Secondary metal coordination using a tetranuclear complex as ligand leading to hexanuclear complexes with enhanced thermal barriers for electron transfer, CCS Chemistry

Recent progress on cyano-bridged transition-metal-based single-molecule magnets and single-chain magnets Novel functional molecular-based magnetic materials, especially some members of the Prussian blue family, have gained significant attention over the past few decades as they can be used beneficially in a variety of scientific fields. Herein, the authors survey the latest developments in cyano-bridged transition-metal-based single-molecule magnets (SMMs) and single-chain magnets (SCMs) research. The cyanide ligand, which has a strong affinity for transition metals, is a popular bridging ligand to construct a variety of molecular-magnetic materials, depending on the type of co-ligand. This review mainly focuses on research into structural topologies and the corresponding SMMs or SCMs. The first section provides a brief introduction into SMM and SCM behavior and important principles and strategies for constructing diverse magnetic materials. The remaining sections provide overviews of significant achievements reported in recent years. In the final section the authors conclude by presenting perspectives on cyanometallate-based SMMs and SCMs and by providing some new insight into this promising area. Jin-Hua Wang, Zhao-Yang Li, Masahiro Yamashita, Xian-He Bu, Recent progress on cyano-bridged transition-metal-based single-molecule magnets and single-chain magnets, Coord. Chem. Rev. 428, 213617 (2021)

Observation of the asphericity of 4f-electron density and its relation to the magnetic anisotropy axis in single-molecule magnets The distribution of electrons in the 4f orbitals of lanthanide ions is often assigned a crucial role in the design of single-molecule magnets, which maintain magnetization in zero external field. Optimal spatial complementarity between the 4f-electron density and the ligand field is key to maximizing magnetic anisotropy, which is an important factor in the ability of lanthanide complexes to display single-molecule magnet behaviour. Here the authors have experimentally determined the electron density distribution in two dysprosium molecular complexes by interpreting high-resolution synchrotron X-ray diffraction with a multipole model. The ground-state 4f-electron density is found to be an oblate ellipsoid, as is often deduced from a simplified Sievers model that assumes a pure |+/-15/2> ground-state doublet for the lanthanide ion. The large equatorial asymmetry—determined by a model wavefunction was found to contain considerable MJ mixing of |+/-11/2> and only 81% of |+/-15/2>. The experimental molecular magnetic easy axes were recovered, and found to deviate by 13.1° and 8.7° from those obtained by ab initio calculations. Chen Gao, Alessandro Genoni, Song Gao, Shangda Jiang, Alessandro Soncini, Jacob Overgaard, Observation of the asphericity of 4f-electron density and its relation to the magnetic anisotropy axis in single-molecule magnets, Nature Chemistry 12, 213–219(2020) compare also Emil Damgaard�Møller, Lennard Krause, Kasper Tolborg, Giovanni Macetti, Dr. Alessandro Genoni, Jacob Overgaard, Quantification of the Magnetic Anisotropy of a Single�Molecule Magnet from the Experimental Electron Density, Angew. Chem. Int. Ed. 59, 21203-21209 (2020)

Molecular Nanomagnets as Qubits with Embedded Quantum-Error Correction The authors show that molecular nanomagnets have a potential advantage in the crucial rush toward quantum computers. Indeed, the sizable number of accessible low-energy states of these systems can be exploited to define qubits with embedded quantum error correction. The authors derive the scheme to achieve this crucial objective and the corresponding sequence of microwave/radiofrequency pulses needed for the error correction procedure. The effectiveness of our approach is shown already with a minimal S = 3/2 unit corresponding to an existing molecule, and the scaling to larger spin systems is quantitatively analyzed. A. Chiesa, E. Macaluso, F. Petiziol, S. Wimberger, P. Santini, and S. Carretta, Molecular Nanomagnets as Qubits with Embedded Quantum-Error Correction, Phys. Chem. Lett. 2020, 11, 20, 8610–8615

Modulating magnetic anisotropy in Ln(III) single-ion magnets using an external electric field Single-molecule magnets have potential uses in several nanotechnology applications, including high-density information storage devices, the realisation of which lies in enhancing the barrier height for magnetisation reversal (Ueff). However, Ln(III) single-ion magnets (SIMs) that have been reported recently reveal that the maximum value of Ueff values that can be obtained by modulating the ligand fields has already been achieved. Here, the authors have explored, using a combination of DFT and ab initio CASSCF calculations, a unique way to enhance the magnetisation reversal barrier using an oriented external electric field in three well-known Ln(III) single-ion magnets: [Dy(Py)5(OtBu)2]+ (1), [Er{N(SiMe3)2}3Cl]− (2) and [Dy(CpMe3)Cl] (3). The study reveals that, for apt molecules, if the appropriate direction and values of the electric fields are chosen, the barrier height can be enhanced by twice that of the limit set by the ligand field. The application of an electric field along the equatorial direction was found to be suitable for oblate shaped Dy(III) complexes and an electric field along the axial direction was found to enhance the barrier height for a prolate Er(III) complex. For complexes 2 and 3, the external electric field was able to magnify the barrier height to 2–3 times that of the original complexes. However, a moderate enhancement was noticed after application of the external electric field in the case of complex 1. This novel non-chemical fine-tuning approach to modulate magnetic anisotropy is expected to yield a new generation of SIMs. Arup Sarkar, Gopalan Rajaraman, Modulating magnetic anisotropy in Ln(III) single-ion magnets using an external electric field, Chem. Sci., 2020,11, 10324-10330

Metal-organic magnets with large coercivity and ordering temperatures up to 242°C Magnets derived from inorganic materials (e.g., oxides, rare-earth–based, and intermetallic compounds) are key components of modern technological applications. Despite considerable success in a broad range of applications, these inorganic magnets suffer several drawbacks, including energetically expensive fabrication, limited availability of certain constituent elements, high density, and poor scope for chemical tunability. A promising design strategy for next-generation magnets relies on the versatile coordination chemistry of abundant metal ions and inexpensive organic ligands. Following this approach, we report the general, simple, and efficient synthesis of lightweight, molecule-based magnets by postsynthetic reduction of preassembled coordination networks that incorporate chromium metal ions and pyrazine building blocks. The resulting metal-organic ferrimagnets feature critical temperatures up to 242°C and a 7500-oersted room-temperature coercivity. Panagiota Perlepe, Itziar Oyarzabal, Aaron Mailman, Morgane Yquel, Mikhail Platunov, Iurii Dovgaliuk,Mathieu Rouzières, Philippe Négrier, Denise Mondieig, Elizaveta A. Suturina, Marie-Anne Dourges, Sébastien Bonhommeau, Rebecca A. Musgrave, Kasper S. Pedersen, Dmitry Chernyshov, Fabrice Wilhelm, Andrei Rogalev, Corine Mathonière, Rodolphe Clérac, Metal-organic magnets with large coercivity and ordering temperatures up to 242°C, Science 370, 587-592 (2020)

Enhancing Magnetic Hysteresis in Single-Molecule Magnets by Ligand Functionalization Design criteria for dysprosium(III) single-molecule magnets (SMMs) with large thermal energy barriers to magnetic reversal have been established and proven, and the challenge to enhance performance is in understanding and controlling electron-vibration coupling that is the origin of magnetic reversal. The authors have prepared an SMM, [Dy(L)2(py)5][BPh4] (HL = (S)-(-)-1-phenylethanol), based on the archetype [Dy(OtBu)2(py)5][BPh4]. Both compounds have similarly large energy barriers of Ueff = 1,130(20) cm−1 and Ueff = 1,250(10) cm−1, and yet the new SMM shows magnetic hysteresis at a far higher temperature of 22 K cf. TH = 4 K for the archetype. Ab initio calculation of the electron-vibration coupling and spin dynamics shows that substitution of the alkoxide ligand in fact enhances relaxation over the energy barrier for the new SMM compared with to the precursor, in agreement with experiment, and that the higher temperature of magnetic hysteresis likely owes to reduced quantum tunneling at low temperatures. Ke-Xin Yu, Jon G.C. Kragskow, You-Song Ding, Yuan-QiZhai, Daniel Reta, Nicholas F. Chilton, Yan-Zhen Zheng, Enhancing Magnetic Hysteresis in Single-Molecule Magnets by Ligand Functionalization, Chem, Volume 6, Issue 7, 9 July 2020, Pages 1777-1793

Molecule-based magnetic materials constructed from paramagnetic organic ligands and two different metal ions This paper reviews the most representative examples of polynuclear complexes containing three spin carriers: a paramagnetic organic ligand (nitronyl-nitroxide, imino-nitroxide, TEMPO, verdazyl and TCNQradical dot-radicals) and two different metal ions (3d-3d’, 3d-4f), focusing on their magnetic properties. The synthetic approaches leading to such compounds are presented. These compounds show a rich structural variety, ranging from discrete species to coordination polymers with various dimensionalities and spin topologies. The general synthetic strategies leading to such compounds are discussed and illustrated. Some 2p-3d-4f complexes have relevance in the field of molecular nanomagnets (Single Molecule Magnets and Single Chain Magnets). Maria G.F. Vaz, Marius Andruh, Molecule-based magnetic materials constructed from paramagnetic organic ligands and two different metal ions, Coordination Chemistry Reviews 427, 2021, 213611

Engineering macrocyclic high performance pentagonal bipyramidal Dy(iii) single-ion magnets The authors generate a new air-stable pseudo-D5h Dy(III) Single-Molecule Magnet (Ueff = 1108 K, TB = 14 K) by combining a weak equatorial ligand field from a macrocyclic LN5 ligand with a strong axial ligand field. Based on their synthetic blueprint, they use ab initio calculations to show the vast scope for macrocyclic engineering of magnetic anisotropy. Angelos B. Canaj, Sourav Dey, Claire Wilson, Oscar Céspedes, Gopalan Rajaraman and Mark Murrie, Engineering macrocyclic high performance pentagonal bipyramidal Dy(iii) single-ion magnets, Chem. Commun., 2020, Advance Article

Constructing clock-transition-based two-qubit gates from dimers of molecular nanomagnets A good qubit must have a coherence time long enough for gate operations to be performed. Avoided level crossings allow for clock transitions in which coherence is enhanced by the insensitivity of the transition to fluctuations in external fields. Because of this insensitivity, it is not obvious how to effectively couple qubits together while retaining clock-transition behavior. Here the authors present a scheme for using a heterodimer of two coupled molecular nanomagnets, each with a clock transition at zero magnetic field, in which all of the gate operations needed to implement one- and two-qubit gates can be implemented with pulsed radio-frequency radiation. The authors show that given realistic coupling strengths between the nanomagnets in the dimer, good gate fidelities can be achieved. The authors identify the primary sources of error in implementing gates and discuss how these may be mitigated, and investigate the range of coherence times necessary for such a system to be a viable platform for implementing quantum computing protocols. Charles A. Collett, Paolo Santini, Stefano Carretta, and Jonathan R. Friedman, Constructing clock-transition-based two-qubit gates from dimers of molecular nanomagnets, Phys. Rev. Research 2, 032037(R) (2020)

Magnetocaloric and barocaloric effects of metal complexes for solid state cooling: Review, trends and perspectives Solid state refrigeration is a viable alternative for the conventional gas-compression technology due to the environmental friendliness of its materials, energy efficiency, and low noise. Research in this field is focused on the development of advanced prototypes and smart materials. This Review focuses on a special family of quantum materials: metal complexes. The author introduces the fundamentals of caloric effects and magnetism of these complexes, discussing their applications at different ranges of temperature, based on different physical mechanisms. At cryogenic temperatures (close to temperature of liquid He), some metal complexes present a huge value of magnetic entropy change, ranging from c.a. 10 J/kgK to c.a. 70 J/kgK (for 7 T of magnetic field change). These values make some metal complexes appealing as cryogenic coolant materials. The author also presents a comprehensive collection of results from the literature, organized on a chart as a function of time, for different classes of metal complexes; those with 3d-3d magnetic interactions, 3d-4f coupling, and 4f-4f interactions. The author observed that those materials that achieved the maximum value of entropy change, i.e., the spin-only value, follow an exponential scaling law with time. This result helps to predict a new class of metal complexes and further outcomes for the field. On the other hand, for a small amount of applied pressure, these materials produce large barocaloric effect around the spin crossover transition (this transition occurs in a wide range of temperature, even close to room temperature). Thus, the author introduces the SCO mechanism and comprehensively review this topic, along with the recent theoretical models and experimental results. The recent results of barocaloric effect are considered enormously significant (56 J/kgK for 0.9 kbar of pressure change, close to room temperature), even in comparison with traditional metallic barocaloric materials. Perspectives for this subject, with discussions about new mechanisms for the models (as the Jahn-Teller distortion and orbital contribution), are also presented. Mario S.Reis, Magnetocaloric and barocaloric effects of metal complexes for solid state cooling: Review, trends and perspectives, Coordination Chemistry Reviews, Volume 417, 15 August 2020, 213357

Exploring the Magnetic Properties of the Largest Single-Molecule Magnets The giant {Mn70} and {Mn84} wheels are the largest nuclearity single-molecule magnets synthesized to date, and understanding their magnetic properties poses a challenge to theory. Starting from first-principles calculations, the authors explore the magnetic properties and excitations in these wheels using effective spin Hamiltonians. They find that the unusual geometry of the superexchange pathways leads to weakly coupled {Mn7} subunits carrying an effective S = 2 spin. The spectrum exhibits a hierarchy of energy scales and massive degeneracies, with the lowest-energy excitations arising from Heisenberg-ring-like excitations of the {Mn7} subunits around the wheel. The authors further describe how weak longer-range couplings can select the precise spin ground-state of the Mn wheels out of the nearly degenerate ground-state band. Henry F. Schurkus, Dianteng Chen, Matthew J. O'Rourke, Hai-Ping Cheng, Garnet Kin-Lic Chan, Exploring the Magnetic Properties of the Largest Single-Molecule Magnets, J. Phys. Chem. Lett. 2020, 11, 10, 3789-3795

Modelling the properties of magnetic clusters with complex structures: how symmetry can help us The purpose of this article is to answer the question of how symmetry helps us to investigate and understand the properties of nanoscopic magnetic clusters with complex structures. The systems of choice will be the three types of polyoxometalates (POMs): (1) POMs containing localised spins; (2) reduced mixed-valence (MV) POMs; (3) partially delocalised POMs in which localised and delocalised subunits coexist and interact. The theoretical tools based on various kinds of symme- try are the following: (1) irreducible tensor operator (ITO) approach based on the so-called "spin-symmetry" and MAGPACK program; (2) group-theoretical assignment of the exchange multiplets based on spin- and point symmetries; (3) group-theoretical classification of the delocalised electronic and electron-vibrational states of MV POMs; (4) general approach (based on spin symmetry) to evaluate the energy levels of large MV clusters and the corresponding MVPACK program; (5) computational approach (employing point symmetry) to solve multidimensional non-adiabatic vibronic problems in the nanoscopic systems realized as VIBPACK software. We made it our goal to avoid a conventional deductive style of presentation. On the contrary, we first consider specially selected complex POMs and then show by what methods and in what way the theoretical problems arising in the description of the properties of these molecules can be properly solved. Boris Tsukerblat, Andrew Paliib, Juan Modesto Clemente-Juan, Eugenio Coronado, Modelling the properties of magnetic clusters with complex structures: how symmetry can help us, INTERNATIONAL REVIEWS IN PHYSICAL CHEMISTRY 2020, VOL. 39, NO. 2, 217-265

Unbiased evaluation of zero-field splitting D parameter in high-spin molecules from DC magnetic data with incomplete powder averaging A simple scheme is presented to account for preferential orientation effects in the DC magnetic response of polycrystalline samples of anisotropic high-spin molecules, like single-molecule magnets. A single additional least-squares parameter is introduced in the fitting of isothermal magnetization vs. field data to describe the leading part of a non-spherical distribution of anisotropy axes. The procedure is shown to afford an accurate D parameter and is potentially applicable whenever complete powder averaging cannot be achieved. Andrea Cornia, Anne-Laure Barra, Giordano Poneti, Erik Tancini, RobertaSessoli, Unbiased evaluation of zero-field splitting D parameter in high-spin molecules from DC magnetic data with incomplete powder averaging, JMMM 510 (2020) 166713

Single-Molecule Toroic Design through Magnetic Exchange Coupling The big data era calls for larger capacity of our hard drive, which in turn depends on the number of magnetic units that store bits of 1 or 0. However, as the density of these units increases, flipping one unit without affecting another becomes more difficult because of undesired magnetic perturbations from the reading/writing heads. Single-molecule toroics (SMTs) that exploit vortex-like magnetic structures are insensitive to homogeneous magnetic fields and hence are promising for next-generation ultra-dense information storage. However, the synthesis of such molecular materials is challenging. Here, we show by using ferromagnetic interactions that this target can be realized in a 16-membered heterometallic cluster {Fe8Dy8}, which shows a stable 4-fold degenerated magnetic toroidal ground state at low temperatures. This is significantly distinguished from the most studied dipole-dipole interaction-based SMTs and demonstrates a promising strategy for the next generation of SMT design. Hao-Lan Zhang, Yuan-Qi Zhai, Lei Qin, Liviu Ungur, Hiroyuki Nojiri, Yan-Zhen Zheng, Single-Molecule Toroic Design through Magnetic Exchange Coupling, Matter, Volume 2, Issue 6, 3 June 2020, Pages 1481-1493

Vibrational coherences in manganese single-molecule magnets after ultrafast photoexcitation Magnetic recording using femtosecond laser pulses has recently been achieved in some dielectric media, showing potential for ultrafast data storage applications. Single-molecule magnets (SMMs) are metal complexes with two degenerate magnetic ground states and are promising for increasing storage density, but remain unexplored using ultrafast techniques. Here the authors have explored the dynamics occurring after photoexcitation of a trinuclear μ3-oxo-bridged Mn(III)-based SMM, whose magnetic anisotropy is closely related to the Jahn-Teller distortion. Ultrafast transient absorption spectroscopy in solution reveals oscillations superimposed on the decay traces due to a vibrational wavepacket. Based on complementary measurements and calculations on the monomer Mn(acac)3, we conclude that the wavepacket motion in the trinuclear SMM is constrained along the Jahn-Teller axis due to the μ3-oxo and µ-oxime bridges. The results provide new possibilities for optical control of the magnetization in SMMs on femtosecond timescales and open up new molecular-design challenges to control the wavepacket motion in the excited state of polynuclear transition-metal complexes. Florian Liedy, Julien Eng, Robbie McNab, Ross Inglis, Thomas J. Penfold, Euan K. Brechin, J. Olof Johansson, Vibrational coherences in manganese single-molecule magnets after ultrafast photoexcitation, Nature Chemistry volume 12, pages452-458(2020)

Dysprosiacarboranes: A New Type of Organometallic Single-Molecule Magnet The dicarbollide ion, nido-C2B9H112- is isoelectronic with cyclopentadienyl. Here the authors make dysprosiacarboranes, namely [(C2B9H11)2Ln(THF)2][Na(THF)5] (Ln = Dy, 1Dy ) and [(THF)3(μ-H)3Li]2[{η5-C6H4(CH2)2C2B9H9 }Dy{η2:η5-C6H4 (CH2)2C2B9H9}2Li] 3Dy and show that dicarbollide ligands impose strong magnetic axiality on the central Dy(III) ion. The effective energy barrier ( U eff ) for loss of magnetisation can be varied by the substitution pattern on the dicarbollide. This is demonstrated by comparing complexes of nido-C2B9H112- and nido-[o-xylylene-C2B9H92- which show U eff of 430(5) K and 804(7) K, respectively. The blocking temperature defined by the open hysteresis temperature of 3Dy reaches 6.8 K. Moreover, the linear complex [Dy(nido-C2B9H11)2]- is predicted to have comparable properties with linear [Dy(CpMe3)2]+ complex. As such, carboranyl ligands and its derivatives may open a new type of organometallic ligands for high-performance single-molecule magnets. Peng-Bo Jin, Yuan-Qi Zhai, Ke-Xin Yu, Richard E. P. Winpenny, Yan-Zhen Zheng, Dysprosiacarboranes: A New Type of Organometallic Single-Molecule Magnet, Angew. Chem. Int. Ed., Volume59, Issue 24 June 8, 2020, Pages 9350-9354

Decoherence in Molecular Electron Spin Qubits: Insights from Quantum Many-Body Simulations Quantum states are described by wave functions whose phases cannot be directly measured but which play a vital role in quantum effects such as interference and entanglement. The loss of the relative phase information, termed decoherence, arises from the interactions between a quantum system and its environment. Decoherence is perhaps the biggest obstacle on the path to reliable quantum computing. Here we show that decoherence occurs even in an isolated molecule, although not all phase information is lost, via a theoretical study of a central electron spin qubit interacting with nearby nuclear spins in prototypical magnetic molecules. The residual coherence, which is molecule-dependent, provides a microscopic rationalization for the nuclear spin diffusion barrier proposed to explain experiments. The contribution of nearby molecules to the decoherence has a nontrivial dependence on separation, peaking at intermediate distances. Molecules that are far away affect only the long-time behavior. Because the residual coherence is simple to calculate and correlates well with the coherence time, it can be used as a descriptor for coherence in magnetic molecules. This work will help establish design principles for enhancing coherence in molecular spin qubits and serve to motivate further theoretical work. Jia Chen, Cong Hu, John F. Stanton, Stephen Hill, Hai-Ping Cheng, Xiao-Guang Zhang, Decoherence in Molecular Electron Spin Qubits: Insights from Quantum Many-Body Simulations, J. Phys. Chem. Lett. 2020, 11, XXX, 2074-2078 see also: P. Vorndamme, J. Schnack, Decoherence of a singlet-triplet superposition state under dipolar interactions of an uncorrelated environment, Phys. Rev. B 101, 075101 (2020)

Adjustable coupling and in situ variable frequency electron paramagnetic resonance probe with loop-gap resonators for spectroscopy up to X-band In standard electron paramagnetic resonance (EPR) spectroscopy, the frequency of an experiment is set and the spectrum is acquired using the magnetic field as the independent variable. There are cases in which it is desirable instead to fix the field and tune the frequency such as when studying avoided level crossings. The have designed and tested an adjustable frequency and variable coupling EPR probe with loop-gap resonators (LGRs) that works at a temperature as low as 1.8 K. The frequency is tuned by adjusting the height of a dielectric piece of sapphire inserted into the gap of an LGR; coupling of the microwave antenna is varied with the height of the antenna above the LGR. Both coupling antenna and dielectric are located within the cryogenic sample chamber, but their motion is controlled with external micrometers located outside the cryostat. The frequency of the LGR (approx. 4 GHz) can be adjusted by more than 1 GHz (>25%). To cover a wide range of frequencies, different LGRs can be designed to cover frequencies up to X-band. The authors demonstrate the operation of their probe by mapping out avoided crossings for the Ni4 molecular nanomagnet to determine the tunnel splittings with high precision. G. Joshi, J. Kubasek, I. Nikolov, B. Sheehan, T. A. Costa, R. A. Allao Cassaro, Jonathan R. Friedman, Adjustable coupling and in situ variable frequency electron paramagnetic resonance probe with loop-gap resonators for spectroscopy up to X-band, Review of Scientific Instruments 91, 023104 (2020)

There is nothing wrong with being soft: using sulfur ligands to increase axiality in a Dy(III) single-ion magnet A new air-stable sulfur-ligated Dy(III) single-ion magnet has been successfully isolated with Ueff = 638 K and hysteresis loops open up to 7 K. In silico studies show that the S co-ligands significantly boost the axiality and that Te- and Se-donors have the potential to further enhance the magnetic properties. Angelos B. Canaj, Sourav Dey, Oscar Cespedes, Claire Wilson, Gopalan Rajaraman, Mark Murrie, There is nothing wrong with being soft: using sulfur ligands to increase axiality in a Dy(III) single-ion magnet, Chem. Commun., 2020, Advance Article

Quantum units from the topological engineering of molecular graphenoids Robustly coherent spin centers that can be integrated into devices are a key ingredient of quantum technologies. Vacancies in semiconductors are excellent candidates, and theory predicts that defects in conjugated carbon materials should also display long coherence times. However, the quantum performance of carbon nanostructures has remained stunted by an inability to alter the sp2-carbon lattice with atomic precision. Here, the authors demonstrate that topological tailoring leads to superior quantum performance in molecular graphene nanostructures. They unravel the decoherence mechanisms, quantify nuclear and environmental effects, and observe spin-coherence times that outclass most nanomaterials. These results validate long-standing assumptions on the coherent behavior of topological defects in graphene and open up the possibility of introducing controlled quantum-coherent centers in the upcoming generation of carbon-based optoelectronic, electronic, and bioactive systems. Federico Lombardi, Alessandro Lodi, Ji Ma, Junzhi Liu, Michael Slota, Akimitsu Narita, William K. Myers, Klaus Müllen, Xinliang Feng, Lapo Bogani, Quantum units from the topological engineering of molecular graphenoids, Science, Vol. 366, Issue 6469, pp. 1107-1110 (2019)

Machine learning guided design of single-molecule magnets for magnetocaloric applications The authors present a data-driven approach to predict entropy changes in small magnetic fields in single-molecule magnets (SMMs) relevant to their application as magnetocaloric refrigerants. They construct a database of SMMs with a representation scheme incorporating aspects related to dimensionality, structure, local coordination environment, ideal total spin of magnetic ions, ligand type, and linking chemistry. They train machine learning models for predicting the entropy change as a function of structure and chemistry and use the models to arrive at the entropy change for hypothetical molecules. They also identify key descriptors that affect the entropy change, thus providing insights into designing tailored SMMs with improved magnetocaloric properties. Ludwig Holleis, B. S. Shivaram, and Prasanna V. Balachandran, Machine learning guided design of single-molecule magnets for magnetocaloric applications, Appl. Phys. Lett. 114, 222404 (2019)

Molecular magnetism: from chemical design to spin control in molecules, materials and devices The field of molecular magnetism is rapidly evolving towards the use of magnetic molecules and molecule-based magnetic materials in physics-driven and nanotechnology-driven fields, in particular molecular spintronics, quantum technologies, metal-organic frameworks (MOFs) and 2D materials. In molecular spintronics, the goal is the development of a new generation of spintronic devices based on molecular materials or, in the longer term, on one or a few molecules. In the area of quantum technologies, the milestones reached in the design of molecular spin qubits with long quantum coherence times and in the implementation of quantum operations have raised expectations for the use of molecular spin qubits in quantum computation. MOFs and 2D materials are two classes of materials for which magnetism has been, until very recently, an elusive property; molecular materials with attractive properties and functionalities are now starting to be developed in both areas. In MOFs, single-molecule magnets and spin crossover complexes can be integrated into the nodes of the framework, within the pores or both, sometimes giving rise to smart magnetic materials or to hybrid materials exhibiting synergistic combinations of properties. 2D molecular-based magnets can provide a platform to study magnetism in the 2D limit and exhibit superior properties compared with their inorganic analogues in terms of chemical stability and tunability. Eugenio Coronado, Molecular magnetism: from chemical design to spin control in molecules, materials and devices, Nature Reviews Materials (2019)

Uncertainty estimates for magnetic relaxation times and magnetic relaxation parameters The use of alternating current (AC) magnetometry to measure magnetic relaxation times is one of the most fundamental measurements for characterising single-molecule magnets (SMMs). These measurements, performed as a function of frequency, temperature and magnetic field, give vital information on the underlying magnetic relaxation process(es) occurring in the material. The magnetic relaxation times are usually fitted to model functions derived from spin-phonon coupling theories that allow characterisation of the mechanisms of magnetic relaxation. The parameters of these relaxation models are then often compared between different molecules in order to find trends with molecular structure that may guide the field to the next breakthrough. However, such meta-analyses of the model parameters are doomed to over-interpretation unless uncertainties in the model parameters can be quantified. Here we determine a method for obtaining uncertainty estimates in magnetic relaxation times from AC experiments, and provide a program called CC-FIT2 for fitting experimental AC data as well as the resulting relaxation times, to obtain relaxation parameters with accurate uncertainties. Applying our approach to three archetypal families of high-performance dysprosium(III) SMMs shows that accounting for uncertainties has a significant impact on the uncertainties of relaxation parameters, and that larger uncertainties appear to correlate with crystallographic disorder in the compounds studied. We suggest that this type of analysis should become routine in the community. Daniel Reta and Nicholas F. Chilton, Uncertainty estimates for magnetic relaxation times and magnetic relaxation parameters, Phys. Chem. Chem. Phys., 2019, Advance Article

No time to read a book? Read this! Two reviews cover the fascination of magnetic molecules from the perspective of physicists. The articles treat single molecules magnets, low-dimensional magnets, spin crossovers, magnetic wheels as well as other compounds. Phenomena such as slow relaxation of magnetization, magnetization tunneling, physical properties depending on frustration, magnetocalorics and quantum phase transitions are discussed. A rich bibliography is provided. Stephen J. Blundell, Molecular Magnets, Contemporary Physics 48 (2008) 275-290 Jürgen Schnack, Large magnetic molecules and what we learn from them, Contemporary Physics 60 (2019) 127-144

Origin of Spin-Dependent Tunneling Through Chiral Molecules The functionality of many biological systems depends on reliable electron transfer with minimal heating. Interestingly, nature realizes electron transport via insulating molecules, in contrast to man-made electronic devices which are based on metals and semiconductors. The high efficiency of electron transfer through these organic molecules is unexpected for tunneling-based transport, and it is one of the most compelling questions in the field. Furthermore, it has been shown that the electron tunneling probability is strongly spin-dependent. Here, the authors demonstrate that the chiral structure of these molecules gives rise to robust coherent electron transfer. The authors introduce spin into the analysis of tunneling through organic helical molecules and show that they support strong spin filtering accompanied by enhanced transmission. Thus, the study resolves two key questions posed by transport measurements through organic molecules. Karen Michaeli, Ron Naaman, Origin of Spin-Dependent Tunneling Through Chiral Molecules, J. Phys. Chem. C 2019, 123, 27, 17043-17048

Air-stable redox-active nanomagnets with lanthanide spins radical-bridged by a metal-metal bond Engineering intramolecular exchange interactions between magnetic metal atoms is a ubiquitous strategy for designing molecular magnets. For lanthanides, the localized nature of 4f electrons usually results in weak exchange coupling. Mediating magnetic interactions between lanthanide ions via radical bridges is a fruitful strategy towards stronger coupling. In this work we explore the limiting case when the role of a radical bridge is played by a single unpaired electron. We synthesize an array of air-stable Ln2@C80(CH2Ph) dimetallofullerenes (Ln2=Y2, Gd2, Tb2, Dy2, Ho2, Er2, TbY, TbGd) featuring a covalent lanthanide-lanthanide bond. The lanthanide spins are glued together by very strong exchange interactions between 4f moments and a single electron residing on the metal-metal bonding orbital. Tb2@C80(CH2Ph) shows a gigantic coercivity of 8.2 Tesla at 5 K and a high 100-s blocking temperature of magnetization of 25.2 K. The Ln-Ln bonding orbital in Ln2@C80(CH2Ph) is redox active, enabling electrochemical tuning of the magnetism. Fupin Liu, Georgios Velkos, Denis S. Krylov, Lukas Spree, Michal Zalibera, Rajyavardhan Ray, Nataliya A. Samoylova, Chia-Hsiang Chen, Marco Rosenkranz, Sandra Schiemenz, Frank Ziegs, Konstantin Nenkov, Aram Kostanyan, Thomas Greber, Anja U. B. Wolter, Manuel Richter, Bernd Büchner, Stanislav M. Avdoshenko & Alexey A. Popov, Air-stable redox-active nanomagnets with lanthanide spins radical-bridged by a metal-metal bond, Nature Communicationsvolume 10, Article number: 571 (2019)

Rare "Janus"-faced {FeII7} single-molecule magnet exhibiting intramolecular ferromagnetic interactions A rare disk-like single-molecule magnet (SMM) exclusively bridged by end-on azides with a spin ground state of S=14 was prepared by the reaction of a divalent Fe(II) precursor with Me3SiN3 under basic conditions. AC magnetic susceptibility studies revealed unusual, "Janus"-faced SMM behavior for the dried and pristine forms of the compound attributed to solvation/de-solvation effects of the coordinated MeCN ligands which leads to alterations in the crystal field and symmetry of the metal ions. DFT calculations confirmed the ferromagnetic nature of the interactions between the FeII spin carriers with the zero-field splitting parameters D=-0.2323 cm-1 and E/D=0.027. The results have important implications for the future study of single-molecule magnets incorporating volatile solvent molecules in the first coordination sphere of the metal ions and their effect on the relaxation dynamics. Dimitris I. Alexandropoulos, Kuduva R. Vignesh, Theocharis C. Stamatatos, Kim R. Dunbar, Rare "Janus"-faced {FeII7} single-molecule magnet exhibiting intramolecular ferromagnetic interactions, Chem. Sci., 2019,10, 1626-1633

Chemistry and Quantum Mechanics in 2019: Give Us Insight and Numbers This Perspective revisits Charles Coulson's famous statement from 1959 "give us insight not numbers" in which he pointed out that accurate computations and chemical understanding often do not go hand in hand. The authors argue that today, accurate wave function based first-principle calculations can be performed on large molecular systems, while tools are available to interpret the results of these calculations in chemical language. This leads us to modify Coulson's statement to "give us insight and numbers". Examples from organic, inorganic, organometallic and surface chemistry as well as molecular magnetism illustrate the points made. Frank Neese, Mihail Atanasov, Giovanni Bistoni, Dimitrios Maganas, Shengfa Ye, Chemistry and Quantum Mechanics in 2019: Give Us Insight and Numbers, J. Am. Chem. Soc.201914172814-2824

A linear cobalt(II) complex with maximal orbital angular momentum from a non-Aufbau ground state Orbital angular momentum is a prerequisite for magnetic anisotropy, although in transition metal complexes it is typically quenched by the ligand field. By reducing the basicity of the carbon donor atoms in a pair of alkyl ligands, the authors synthesized a cobalt(II) dialkyl complex, Co(C(SiMe2ONaph)3)2 (where Me is methyl and Naph is a naphthyl group), wherein the ligand field is sufficiently weak that interelectron repulsion and spin-orbit coupling play a dominant role in determining the electronic ground state. Assignment of a non-Aufbau (dx2-y2, dxy)3(dxz, dyz)3(dz2)1 electron configuration is supported by dc magnetic susceptibility data, experimental charge density maps, and ab initio calculations. Variable-field far-infrared spectroscopy and ac magnetic susceptibility measurements further reveal slow magnetic relaxation via a 450-wave number magnetic excited state. Philip C. Bunting, Mihail Atanasov, Emil Damgaard-Moller, Mauro Perfetti, Iris Crassee, Milan Orlita, Jacob Overgaard, Joris van Slageren, Frank Neese, Jeffrey R. Long, A linear cobalt(II) complex with maximal orbital angular momentum from a non-Aufbau ground state, Science 21 Dec 2018, Vol. 362, Issue 6421, eaat7319

First-principles many-body models for electron transport through molecular nanomagnets Impressive advances in the field of molecular spintronics allow one to study electron transport through individual magnetic molecules embedded between metallic leads in the purely quantum regime of single electron tunneling. Besides fundamental interest, this experimental setup, in which a single molecule is manipulated by electronic means, provides the elementary units of possible forthcoming technological applications, ranging from spin valves to transistors and qubits for quantum information processing. Theoretically, while for weakly correlated molecular junctions established first-principles techniques do enable the system-specific description of transport phenomena, methods of similar power and flexibility are still lacking for junctions involving strongly correlated molecular nanomagnets. Here the authors propose an efficient scheme based on the ab initio construction of material-specific Hubbard models and on the master-equation formalism. The authors apply this approach to a representative case, the {Ni2} molecular spin dimer, in the regime of weak molecule-electrode coupling, the one relevant for quantum-information applications. The approach allows to study in a realistic setting many-body effects such as current suppression and negative differential conductance. The authors think that this method has the potential for becoming a very useful tool for describing transport phenomena in strongly correlated molecules. A. Chiesa, E. Macaluso, P. Santini, S. Carretta, and E. Pavarini, First-principles many-body models for electron transport through molecular nanomagnets, Phys. Rev. B 99, 235145 (2019)

161Dy Time-Domain Synchrotron Mössbauer Spectroscopy for Investigating Single-Molecule Magnets Incorporating Dy Ions Time-domain synchrotron Mössbauer spectroscopy (SMS) based on the Mössbauer effect of 161Dy has been used to investigate the magnetic properties of a DyIII-based single-molecule magnet (SMM). The magnetic hyperfine field of [Dy(Cy3PO)2(H2O)5]Br3 2(Cy3PO) 2H2O 2EtOH is with B=582.3T significantly larger than that of the free-ion DyIII with a 6H15/2 ground state. This difference is attributed to the influence of the coordinating ligands on the Fermi contact interaction between the s and 4f electrons of the DyIII ion. This study demonstrates that 161Dy SMS is an effective local probe of the influence of the coordinating ligands on the magnetic structure of Dy-containing compounds. Dipl.-Phys. Lena Scherthan, Dr. Sebastian F. M. Schmidt, Dipl.-Biophys. Hendrik Auerbach, Dipl.-Phys. Tim Hochdörffer, Dr. Juliusz A. Wolny, Dr. Wenli Bi, Dr. Jiyong Zhao, Dr. Michael Y. Hu, Dr. Tom Toellner, Dr. E. Ercan Alp, Dr. Dennis E. Brown, Dr. Christopher E. Anson, Prof. Annie K. Powell, Prof. Volker Schünemann, 161Dy Time-Domain Synchrotron Mössbauer Spectroscopy for Investigating Single-Molecule Magnets Incorporating Dy Ions, Angew. Chem. Int. Ed. 58, 2019, 3444-3449 See also this press release.

Insight into D6h Symmetry: Targeting Strong Axiality in Stable Dysprosium(III) Hexagonal Bipyramidal Single�Ion Magnets Following a novel synthetic strategy where the strong uniaxial ligand field generated by the Ph3SiO- (Ph3SiO- = anion of triphenylsilanol) and the 2,4-di-tBu-PhO- (2,4-di-tBu-PhO- = anion of 2,4-di-tert-butylphenol) ligands combined with the weak equatorial field of the ligand LN6, leads to [DyIII(LN6)(2,4-di-tBu-PhO)2](PF6) (1), [DyIII(LN6)(Ph3SiO)2](PF6) (2) and [DyIII(LN6)(Ph3SiO)2](BPh4) (3) hexagonal bipyramidal dysprosium(III) single-molecule magnets (SMMs) with high anisotropy barriers of Ueff = 973 K for 1, Ueff = 1080 K for 2 and Ueff = 1124 K for 3 under zero applied dc field. Ab initio calculations predict that the dominant magnetization reversal barrier of these complexes expands up to the 3rd Kramers doublet, thus revealing for the first time the exceptional uniaxial magnetic anisotropy that even the six equatorial donor atoms fail to negate, opening up the possibility to other higher-order symmetry SMMs. Mark Murrie, Angelos Canaj, Sourav Dey, Emma Regincos Marti, Claire Wilson, Gopalan Rajaraman, Insight into D6h Symmetry: Targeting Strong Axiality in Stable Dysprosium(III) Hexagonal Bipyramidal Single-Ion Magnets, Angew. Chem. Int. Ed. (2019) accepted article

Quantum hardware simulating four-dimensional inelastic neutron scattering Magnetic molecules, modelled as finite-size spin systems, are test-beds for quantum phenomena1 and could constitute key elements in future spintronics devices, long-lasting nanoscale memories or noise-resilient quantum computing platforms. Inelastic neutron scattering is the technique of choice to probe them, characterizing molecular eigenstates on atomic scales. However, although large magnetic molecules can be controllably synthesized, simulating their dynamics and interpreting spectroscopic measurements is challenging because of the exponential scaling of the required resources on a classical computer. Here, the authors show that quantum computers have the potential to efficiently extract dynamical correlations and the associated magnetic neutron cross-section by simulating prototypical spin systems on a quantum hardware. A. Chiesa, F. Tacchino, M. Grossi, P. Santini, I. Tavernelli, D. Gerace, S. Carretta, Quantum hardware simulating four-dimensional inelastic neutron scattering, Nature Physics 15, 455-459 (2019)

Giant Barocaloric Effect at the Spin Crossover Transition of a Molecular Crystal The first experimental evidence for a giant, conventional barocaloric effect (BCE) associated with a pressure-driven spin crossover transition near room temperature is provided. Magnetometry, neutron scattering, and calorimetry are used to explore the pressure dependence of the SCO phase transition in polycrystalline samples of protonated and partially deuterated [FeL2][BF4]2 [L=2,6-di(pyrazol-1-yl)pyridine] at applied pressures of up to 120 MPa (1200 bar). The data indicate that, for a pressure change of only 0-300 bar (0-30 MPa), an adiabatic temperature change of 3 K is observed at 262 K or 257 K in the protonated and deuterated materials, respectively. This BCE is equivalent to the magnetocaloric effect (MCE) observed in gadolinium in a magnetic field change of 0-1 Tesla. The work confirms recent predictions that giant, conventional BCEs will be found in a wide range of SCO compounds. Steven P. Vallone, Anthony N. Tantillo, Antonio M. dos Santos, Jamie J. Molaison, Rafal Kulmaczewski, Antonin Chapoy, Pezhman Ahmadi, Malcolm A. Halcrow, Karl G. Sandeman, Giant Barocaloric Effect at the Spin Crossover Transition of a Molecular Crystal, Adv. Mater. 2019, 1807334

After MAGPACK there comes VIBPACK A FORTRAN code based on a new powerful and efficient computational approach to solve multidimensional dynamic Jahn-Teller and pseudo Jahn-Teller problems is presented. This symmetry-assisted approach constituting a theoretical core of the program is based on the full exploration of the point symmetry of the electronic and vibrational states. The authors also report some selected examples of increasing complexity aimed to display the theoretical background as well as the advantages and capabilities of the program to evaluate of the energy pattern, magnetic and optical properties of large multimode vibronic systems. Juan M. Clemente-Juan, Andrew Palii, Boris Tsukerblat, Eugenio Coronado, VIBPACK: A package to treat multidimensional electron-vibrational molecular problems with application to magnetic and optical properties, Journal of Computational Chemistry 2018, 39, 1815-1827

Neutron Scattering in Coordination Chemistry The application of four dimensional inelastic neutron scattering to coordination chemistry is demonstrated in a special issue of the European Journal of Inorganic Chemistry by the guest editors John A. Stride, Wendy L. Queen, and Antonio Romerosa. See e.g. the following articles. Elena Garlatti, Alessandro Chiesa, Tatiana Guidi, Giuseppe Amoretti, Paolo Santini, Stefano Carretta, Unravelling the Spin Dynamics of Molecular Nanomagnets with Four-Dimensional Inelastic Neutron Scattering, Eur. J. Inorg. Chem. 2019 (2019) 1106-1118 Krunoslav Prša, Oliver Waldmann, Inelastic Neutron Scattering Intensities of Ferromagnetic Cluster Spin Waves, Eur. J. Inorg. Chem. 2019 (2019) 1128-1141

Electric field modulation of magnetic exchange in molecular helices The possibility to operate on magnetic materials through the application of electric rather than magnetic fields - promising faster, more compact and energy efficient circuits - continues to spur the investigation of magnetoelectric effects. Symmetry considerations, in particular the lack of an inversion centre, characterize the magnetoelectric effect. In addition, spin-orbit coupling is generally considered necessary to make a spin system sensitive to a charge distribution. However, a magnetoelectric effect not relying on spin-orbit coupling is appealing for spin-based quantum technologies. Here, we report the detection of a magnetoelectric effect that we attribute to an electric field modulation of the magnetic exchange interaction without atomic displacement. The effect is visible in electron paramagnetic resonance absorption of molecular helices under electric field modulation and confirmed by specific symmetry properties and spectral simulation. Maria Fittipaldi, Alberto Cini, Giuseppe Annino, Alessandro Vindigni, Andrea Caneschi, Roberta Sessoli, Electric field modulation of magnetic exchange in molecular helices, Nature Materials, volume 18, pages329-334 (2019)

Cages on a plane: a structural matrix for molecular 'sheets' A family of heterometallic Anderson-type 'wheels' of general formula [MIII2MII5(hmp)12]4+ (MIII = Cr or Al and MII = Ni or Zn, Hhmp = 2-pyridinemethanol) has been extended by the authors to include MIII = Cr or Al and MII = Co, Fe, Mn or Cu, affording five new species of formulae [Cr2Co5(hmp)12](ClO4)4 (1), [Cr2Fe5(hmp)12](ClO4)4 (2), [Cr2Mn5(hmp)12](ClO4)4 (3), [Cr2Cu5(hmp)12](ClO4)2(NO3)2 (4) and [Al2Co5(hmp)12](ClO4)4 (5). As per previous family members, the metallic skeleton common to the cations of 1-5 describes a centred hexagon with the two MIII sites disordered around the outer wheel, with the exception of compound 4 where the CuII sites are localised. A structurally related, but enlarged planar disc possessing a [MIII6MII] hexagon capped on each edge by a CuII ion can be formed, but only when MIII = Al and MII = Cu. In [AlIII6CuII7(OH)12(hmp)12](ClO4)6(NO3)2 (6) the Anderson moiety contains a central, symmetry-imposed octahedral CuII ion surrounded by a wheel of AlIII ions. Solid-state dc susceptibility and magnetisation measurements reveal the presence of competing exchange interactions in 1-5, and very weak antiferromagnetic exchange between the CuII ions in 6 which may be intra- and/or intermolecular in nature. Hector W. L. Fraser, Gary S. Nichol, Amgalanbaatar Baldansuren, Eric J. L. McInnes, Euan K. Brechin, Cages on a plane: a structural matrix for molecular 'sheets', Dalton Trans., 2018, 47, 15530-15537

Switchable cobalt coordination polymers: Spin crossover and valence tautomerism Electronically labile, or switchable, cobalt coordination polymers exhibit reversible spin crossover (SCO) or valence tautomeric (VT) transitions upon the application of an external stimulus, such as temperature variation. Spin crossover transitions at pseudo-octahedral cobalt(II) centers with an appropriate ligand field involve a heating-induced transition from the low-spin to high-spin electronic configurations. Valence tautomeric transitions are most commonly observed for cobalt-dioxolene systems, which undergo an intramolecular electron transfer and concomitant spin transition at the cobalt center, from low-spin-cobalt(III)-catecholate at low temperature to high-spin-cobalt(II)-semiquinonate upon heating. The VT transition can also be induced by light, while the cobalt(II) SCO transition cannot. Incorporation of these switchable moieties into coordination polymers (CPs) is generally achieved using polytopic nitrogen-donor linking ligands. All but one of the switchable cobalt CPs that have been structurally characterized are 1D chains, most of which exhibit VT transitions rather than SCO. There is a single example of a switchable 2D cobalt CP where VT cobalt-dioxolene moieties are linked by a tetratopic nitrogen-donor bridging ligand. Efforts to confer the VT properties to compounds suitable for applications as materials or in devices have mainly focused on the incorporation of the 1D chain VT CPs into nano- and microparticles, in which the VT transition is generally maintained. Valence tautomeric nanoparticles synthesized from 1D chain CPs have been grafted on to gold surfaces as self-assembled monolayers. Olga Drath, Colette Boskovic, Switchable cobalt coordination polymers: Spin crossover and valence tautomerism, Coordination Chemistry Reviews, Volume 375, 2018, Pages 256-266

Electric Field Control of Spins in Molecular Magnets Coherent control of individual molecular spins in nanodevices is a pivotal prerequisite for fulfilling the potential promised by molecular spintronics. By applying electric field pulses during time-resolved electron spin resonance measurements, the authors measure the sensitivity of the spin in several antiferromagnetic molecular nanomagnets to external electric fields. They find a linear electric field dependence of the spin states in {Cr7Mn}, an antiferromagnetic ring with a ground-state spin of S=1, and in a frustrated {Cu3} triangle.Conversely, the antiferromagnetic ring {Cr7Ni}, isomorphic with {Cr7Mn} but with S=1/2, does not exhibit a detectable effect. The authors propose that the spin-electric field coupling may be used for selectively controlling individual molecules embedded in nanodevices. Junjie Liu, Jakub Mrozek, William K. Myers, Grigore A. Timco, Richard E.P. Winpenny, Benjamin Kintzel, Winfried Plass, and Arzhang Ardavan, Electric Field Control of Spins in Molecular Magnets, Phys. Ref. Lett. 122, 037202 (2019)

Insights into Magnetic Interactions in a Monodisperse Gd12Fe14 Metal Cluster The largest Ln-Fe metal cluster {Gd12Fe14} and the core-shell monodisperse metal cluster of {Gd12Fe14}@SiO2 were prepared. Experimental and theoretical studies on the magnetic properties reveal that encapsulation of one cluster into one silica nanosphere not only effectively decreases intermolecular magnetic interactions but also significantly increases the zero-field splitting effect of the outer layer Fe3+ ions. Xiu-Ying Zheng, Hui Zhang, Zhenxing Wang, Pengxin Liu, Ming-Hao Du, Ying-Zi Han, Rong-Jia Wei, Zhong-Wen Ouyang, Xiang-Jian Kong, Gui-Lin Zhuang, La-Sheng Long, Lan-Sun Zheng, Insights into Magnetic Interactions in a Monodisperse Gd12Fe14 Metal Cluster, Angew. Chem. Int. Ed. 56, 11475-11479 (2017)

Molecular electronic spin qubits from a spin-frustrated trinuclear copper complex A new trinuclear copper(II) complex was synthesized and characterized by experimental as well as theoretical methods. This complex exhibits a strong antiferromagnetic coupling (J = -298 cm-1) between the copper(II) ions, mediated by the N-N diazine bridges of the tritopic ligand, leading to a spin-frustrated system. This compound shows a T2 coherence time of 340 ns in frozen pyridine solution, which extends to 591 ns by changing the solvent to pyridine-d5. Hence, the presented compound is a promising candidate as a building block for molecular spintronics. Benjamin Kintzel, Michael Böhme, Junjie Liu, Anja Burkhardt, Jakub Mrozek, Axel Buchholz, Arzhang Ardavan, Winfried Plass, Molecular electronic spin qubits from a spin-frustrated trinuclear copper complex, Chem. Commun., 2018,54, 12934-12937

Element specific determination of the magnetic properties of two macrocyclic tetranuclear 3d-4f complexes with a Cu3Tb core by means of X-ray magnetic circular dichroism (XMCD) We apply X-ray magnetic circular dichroism to study the internal magnetic structure of two very promising star shaped macrocyclic complexes with a CuII3TbIII core. These complexes are rare examples prepared with a macrocyclic ligand that show indications of SMM (Single Molecule Magnet) behavior, and they differ only in ring size: one has a propylene linked macrocycle, [CuII3TbIII(LPr)(NO3)2(MeOH)(H2O)2](NO3) 3H2O (nickname: Cu3Tb(LPr)), and the other has the butylene linked analogue, [CuII3TbIII(LBu)(NO3)2(MeOH)(H2O)](NO3) 3H2O (nickname: Cu3Tb(LBu)). We analyze the orbital and spin contributions to the Cu and Tb ions quantitatively by applying the spin and orbital sum rules concerning the L2 (M4)/L3 (M5) edges. In combination with appropriate ligand field simulations, we demonstrate that the Tb(III) ions contribute with high orbital magnetic moments to the magnetic anisotropy, whereas the ligand field determines the easy axis of magnetization. Furthermore, we confirm that the Cu(II) ions in both molecules are in a divalent valence state, the magnetic moments of the three Cu ions appear to be canted due to 3d-3d intramolecular magnetic interactions. For Cu3Tb(LPr), the corresponding element specific magnetization loops reflect that the Cu(II) contribution to the overall magnetic picture becomes more important as the temperature is lowered. This implies a low value for the 3d-4f coupling. K. Balinski, L. Schneider, J. Wöllermann, A. Buling, L. Joly, C. Piamonteze, H. L. C. Feltham, S. Brooker, A. K. Powell, B. Delley and K. Kuepper, Element specific determination of the magnetic properties of two macrocyclic tetranuclear 3d-4f complexes with a Cu3Tb core by means of X-ray magnetic circular dichroism (XMCD), Phys. Chem. Chem. Phys., 2018, g20, 21286-21293 Along similar lines compare A. Alhassanat, C. Gamer, A. Rauguth, A. A. Athanasopoulou, J. Sutter, C. Luo, H. Ryll, F. Radu, A. A. Sapozhnik, T. Mashoff, E. Rentschler, and H. J. Elmers, Element-specific magnetic properties of mixed 3d-4f metallacrowns, Phys. Rev. B 98, 064428 (2018)

Novel Magnetic Nanostructures A sharp increase in research activity in the field of magnetic nanostructures prompted us to present new scientific results obtained in the last decade. Magnetic nanoscale materials are the key to the future of the storage industry. The demand for higher density of information storage and the emergence of completely new technologies call for entirely new types of magnetic nanostructures. This book provides the latest research on novel magnetic nanostructures, including molecular nanomagnets, magnetic dendrimers, self-assembling magnetic nanoparticles, nanoparticles with spin-crossover properties, multifunctional nanostructures, and much more. Nanomagnets based on d- and f-block coordination compounds as single-molecule magnets demonstrate properties that are suitable for quantum information processing. The book reviews the synthesis, design, characterization, and detection of unusual properties in new magnetic nanostructures. It discusses the physical properties and potential industry-oriented applications such as magnetic data storage, magnetic sensors, magnetic tunnel junctions, spintronics, and biomedical applications. This book is primarily intended for graduate students, but will be of great interest also to all scientists and engineers working in field of magnetic nanoscale materials. Editor(s): Natalia Domracheva, Maria Caporali, Eva Rentschler, Novel Magnetic Nanostructures, Elsevier, 2018, ISBN 9780128135945,

The race goes on: record for ground state spin now at S=91 After the successful synthesis and characterization of a toric cluster with S=60 (see npj Quantum Materials 3 (2018) 10 and below on this page) a new cluster was produced featuring an S=91 ground state. The detailed analysis of magnetic interactions in such giant molecules is difficult both because the synthesis of such compounds is challenging and the number of energy levels increases exponentially with the magnitude and number of spins. The authors isolated a {Ni21Gd20} nanocage with a large number of energy levels (approx 5 x 1030) and used quantum Monte Carlo (QMC) simulations to perform a detailed analysis of magnetic interactions. Based on magnetization measurements above 2 K, the QMC simulations predicted very weak ferromagnetic interactions that would give a record S=91 spin ground state. Low-temperature measurements confirm the spin ground state but suggest a more complex picture due to the single ion anisotropy; this has also been modeled using the QMC approach. The high spin and large number of low-lying states lead to a large low-field magnetic entropy for this material. Wei-Peng Chen, Jared Singleton, Lei Qin, Agustin Camon, Larry Engelhardt, Fernando Luis, Richard E. P. Winpenny & Yan-Zhen Zheng, Quantum Monte Carlo simulations of a giant {Ni21Gd20} cage with a S=91 spin ground state, Nature Communications 9, Article number: 2107 (2018)

Hyperfine-Interaction-Driven Suppression of Quantum Tunneling at Zero Field in a Holmium(III) Single-Ion Magnet An extremely rare non-Kramers holmium(III) single-ion magnet (SIM) is reported to be stabilized in the pentagonal-bipyramidal geometry by a phosphine oxide with a high energy barrier of 237(4)/cm. The suppression of the quantum tunneling of magnetization (QTM) at zero field and the hyperfine structures originating from field-induced QTMs can be observed even from the field-dependent alternating-current magnetic susceptibility in addition to single-crystal hysteresis loops. These dramatic dynamics were attributed to the combination of the favorable crystal-field environment and the hyperfine interactions arising from 165Ho (I=7/2) with a natural abundance of 100 %. Yan-Cong Chen, Jun-Liang Liu, Wolfgang Wernsdorfer, Dan Liu, Liviu F. Chibotaru, Xiao-Ming Chen, Ming-Liang Tong, Hyperfine-Interaction-Driven Suppression of Quantum Tunneling at Zero Field in a Holmium(III) Single-Ion Magnet, Angew. Chem. Int. Ed. 56, 2017, 4996-5000 See also: Jun-Liang Liu, Yan-Cong Chen, Ming-Liang Tong, Symmetry strategies for high performance lanthanide-based single-molecule magnets, Chem. Soc. Rev., 2018, 47, 2431-2453

Modeling Spin Interactions in a Triangular Cobalt(II) Complex with Triaminoguanidine Ligand Framework: Synthesis, Structure, and Magnetic Properties The new tritopic triaminoguanidine-based ligand 1,2,3-tris[(pyridine-2-ylmethylidene)amino]guanidine (H2pytag) was synthesized. The reaction of a mixture of cobalt(II) chloride and cobalt(II) perchlorate with the ligand H2pytag in pyridine solution leads to the formation of the trinuclear cobalt(II) complex [Co3(pytag)(py)6Cl3]ClO4. Three octahedrally coordinated high-spin cobalt(II) ions are linked through the bridging triaminoguanidine backbone of the ligand leading to an almost equilateral triangular arrangement. The magnetic properties of the complex were investigated by magnetic measurements, variable-temperature, variable-field magnetic circular dichroism (MCD) spectroscopy, and density functional theory as well as ab initio calculations. A rather strong antiferromagnetic exchange interaction between the cobalt(II) centers of ca. -12/cm is determined together with a strong local anisotropy. The single-ion anisotropy of all three cobalt(II) centers is found to be easy-plane, which coincides with the tritopic ligand plane. MCD measurements and theoretical investigations demonstrate the presence of rhombic distortion of the local Co surrounding. Daniel Plaul, Michael Böhme, Serghei Ostrovsky, Zbigniew Tomkowicz, Helmar Görls, Wolfgang Haase, Winfried Plass, Modeling Spin Interactions in a Triangular Cobalt(II) Complex with Triaminoguanidine Ligand Framework: Synthesis, Structure, and Magnetic Properties, Inorg. Chem., 2018, 57 (1), pp 106-119 See also: Eike T. Spielberg, Aksana Gilb, Daniel Plaul, Daniel Geibig, David Hornig, Dirk Schuch, Axel Buchholz, Arzhang Ardavan, Winfried Plass, A Spin-Frustrated Trinuclear Copper Complex Based on Triaminoguanidine with an Energetically Well-Separated Degenerate Ground State, Inorg. Chem., 2015, 54 (7), pp 3432-3438

Robust and Selective Switching of an FeIII Spin-Crossover Compound on Cu2N/Cu(100) with Memristance Behavior The switching between two spin states makes spin-crossover molecules on surfaces very attractive for potential applications in molecular spintronics. Using scanning tunneling microscopy, the successful deposition of [Fe(pap)2]+ (pap = N-2-pyridylmethylidene-2-hydroxyphenylaminato) molecules on Cu2N/Cu(100) surface is evidenced. The deposited FeIII spin-crossover compound is controllably switched between three different states, each of them exhibiting a characteristic tunneling conductance. The conductance is therefore employed to readily read the state of the molecules. A comparison of the experimental data with the results of density functional theory calculations reveals that all Fe(pap)2 molecules are initially in their high-spin state. The two other states are compatible with the low-spin state of the molecule but differ with respect to their coupling to the substrate. As a proof of concept, the reversible and selective nature of the switching is used to build a two-molecule memory. Torben Jasper-Toennies, Manuel Gruber, Sujoy Karan, Hanne Jacob, Felix Tuczek , Richard Berndt, Robust and Selective Switching of an FeIII Spin-Crossover Compound on Cu2N/Cu(100) with Memristance Behavior, Nano Lett. 2017, 11, 6613-6619

Highly Ordered Surface Self-Assembly of Fe4 Single Molecule Magnets Single molecule magnets (SMMs) have attracted considerable attention due to low-temperature magnetic hysteresis and fascinating quantum effects. The investigation of these properties requires the possibility to deposit well-defined monolayers or spatially isolated molecules within a well-controlled adsorption geometry. Here the authors present a successful fabrication of self-organized arrays of Fe4 SMMs on hexagonal boron nitride (h-BN) on Rh(111) as template. Using a rational design of the ligand shell optimized for surface assembly and electrospray as a gentle deposition method, we demonstrate how to obtain ordered arrays of molecules forming perfect hexagonal superlattices of tunable size, from small islands to an almost perfect monolayer. High-resolution low temperature scanning tunneling microscopy (STM) reveals that the Fe4 molecule adsorbs on the substrate in a flat geometry, meaning that its magnetic easy axis is perpendicular to the surface. By scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations, we infer that the majority- and minority-spin components of the spin-split lowest unoccupied molecular orbital (LUMO) can be addressed separately on a submolecular level. Philipp Erler, Peter Schmitt, Nicole Barth, Andreas Irmler, Samuel Bouvron, Thomas Huhn, Ulrich Groth, Fabian Pauly, Luca Gragnaniello, Mikhail Fonin, Highly Ordered Surface Self-Assembly of Fe4 Single Molecule Magnets, Nano Lett., 2015, 15, 4546-4552

Mössbauer spectroscopy of a monolayer of single molecule magnets The use of single molecule magnets (SMMs) as cornerstone elements in spintronics and quantum computing applications demands that magnetic bistability is retained when molecules are interfaced with solid conducting surfaces. Here, the authors employ synchrotron Mössbauer spectroscopy to investigate a monolayer of a tetrairon(III) (Fe4) SMM chemically grafted on a gold substrate. At low temperature and zero magnetic field, the authors observe the magnetic pattern of the Fe4 molecule, indicating slow spin fluctuations compared to the Mössbauer timescale. Significant structural deformations of the magnetic core, induced by the interaction with the substrate, as predicted by ab initio molecular dynamics, are also observed. However, the effects of the modifications occurring at the individual iron sites partially compensate each other, so that slow magnetic relaxation is retained on the surface. Interestingly, these deformations escaped detection by conventional synchrotron-based techniques, like X-ray magnetic circular dichroism, thus highlighting the power of synchrotron Mössbauer spectroscopy for the investigation of hybrid interfaces. Alberto Cini, Matteo Mannini, Federico Totti, Maria Fittipaldi, Gabriele Spina, Aleksandr Chumakov, Rudolf Rüffer, Andrea Cornia, Roberta Sessoli, Mössbauer spectroscopy of a monolayer of single molecule magnets, Nature Communications 9, 480 (2018)

Myriam Sarachik looks back in Annual Review of Condensed Matter Physics This autobiographical narrative offers a brief account of Prof. Sarachik's journey and adventures in condensed matter physics (a.k.a. solid state physics) and some of the personal events that shaped her life and career: early years in Europe, family's escape from the Nazis, growing up in Cuba, the difficult road into a field that was essentially closed to women, a personal disaster that knocked the wind out of her sails for more than a decade, and her return to a successful career in physics. In closing, she argues that, although we have made remarkable progress, we know but a thimble-full in our inexhaustible search for an understanding of the laws of nature. Myriam P. Sarachik, Pushing Boundaries: My Personal and Scientific Journey, Annual Review of Condensed Matter Physics 9, 1-15 (2018)

Effects of uniaxial pressure on the quantum tunneling of magnetization in a high-symmetry Mn12 single-molecule magnet The symmetry of single-molecule magnets dictates their spin quantum dynamics, influencing how such systems relax via quantum tunneling of magnetization (QTM). By reducing a system's symmetry, through the application of a magnetic field or uniaxial pressure, these dynamics can be modified. The authors report measurements of the magnetization dynamics of a crystalline sample of a high-symmetry Mn12 single-molecule magnet as a function of uniaxial pressure applied either parallel or perpendicular to the sample's "easy" magnetization axis. At temperatures between 1.8 and 3.3 K, magnetic hysteresis loops exhibit the characteristic steplike features that signal the occurrence of QTM. After applying uniaxial pressure to the sample in situ, both the magnitude and field position of the QTM steps changed. The step magnitudes were observed to grow as a function of pressure in both arrangements of pressure, while pressure applied along (perpendicular to) the sample's easy axis caused the resonant-tunneling fields to increase (decrease). These observations were compared with simulations in which the system's Hamiltonian parameters were changed. From these comparisons, we determined that parallel pressure induces changes to the second-order axial anisotropy parameter as well as either the fourth-order axial or fourth-order transverse parameter, or to both. In addition, we find that pressure applied perpendicular to the easy axis induces a rhombic anisotropy that can be understood as deriving from a symmetry-breaking distortion of the molecule. James H. Atkinson, Adeline D. Fournet, Lakshmi Bhaskaran, Yuri Myasoedov, Eli Zeldov, Enrique del Barco, Stephen Hill, George Christou, and Jonathan R. Friedman, Effects of uniaxial pressure on the quantum tunneling of magnetization in a high-symmetry Mn12 single-molecule magnet, Phys. Rev. B 95, 184403 (2017)

High spin cycles: topping the spin record for a single molecule verging on quantum criticality The cyclisation of a short chain into a ring provides fascinating scenarios in terms of transforming a finite array of spins into a quasi-infinite structure. If frustration is present, theory predicts interesting quantum critical points, where the ground state and thus low-temperature properties of a material change drastically upon even a small variation of appropriate external parameters. This can be visualised as achieving a very high and pointed summit where the way down has an infinity of possibilities, which by any parameter change will be rapidly chosen, in order to reach the final ground state. The authors of the article in the new Nature journal npj Quantum Materials report a mixed 3d/4f cyclic coordination cluster that turns out to be very near or even at such a quantum critical point. It has a ground state spin of S=60, the largest ever observed for a molecule (120 times that of a single electron). The molecule forms a nano-torus with alternating gadolinium and iron ions with a nearest neighbour Fe-Gd coupling and a frustrating next-nearest neighbour Fe-Fe coupling. Such a spin arrangement corresponds to a cyclic delta or saw-tooth chain, which can exhibit unusual frustration effects. In the present case, the quantum critical point bears a 'flatland' of tens of thousands of energetically degenerate states between which transitions are possible at no energy costs with profound caloric consequences. Entropy-wise the energy flatland translates into the pointed summit overlooking the entropy landscape. Going downhill several target states can be reached depending on the applied physical procedure which offers new prospects for addressability. Amer Baniodeh, Nicola Magnani, Yanhua Lan, Gernot Buth, Christopher E. Anson, Johannes Richter, Marco Affronte, Jürgen Schnack, Annie K. Powell, High spin cycles: topping the spin record for a single molecule verging on quantum criticality, npj Quantum Materials 3 (2018) 10 For a structurally related compound see also: Lei Qin, Jared Singleton, Wei-Peng Chen, Hiroyuki Nojiri, Larry Engelhardt, Richard E. P. Winpenny, Yan-Zhen Zheng, Quantum Monte Carlo Simulations and High-Field Magnetization Studies of Antiferromagnetic Interactions in a Giant Hetero-Spin Ring, Angew. Chem. Int. Ed. 56, 2017, 16571-16574

Dynamical spin accumulation in large-spin magnetic molecules The frequency-dependent transport through a nanodevice containing a large-spin magnetic molecule is studied theoretically in the Kondo regime. Specifically, the effect of magnetic anisotropy on dynamical spin accumulation is of primary interest. Such accumulation arises due to finite components of frequency-dependent conductance that are off diagonal in spin. Here, employing the Kubo formalism and the numerical renormalization group method, the authors demonstrate that the dynamical transport properties strongly depend on the relative orientation of spin moments in electrodes of the device, as well as on intrinsic parameters of the molecule. In particular, the effect of dynamical spin accumulation is found to be greatly affected by the type of magnetic anisotropy exhibited by the molecule, and it develops for frequencies corresponding to the Kondo temperature. For the parallel magnetic configuration of the device, the presence of dynamical spin accumulation is conditioned by the interplay of ferromagnetic-lead-induced exchange field and the Kondo correlations. Anna Plominska, Ireneusz Weymann, Maciej Misiorny, Dynamical spin accumulation in large-spin magnetic molecules, Phys. Rev. B 97, 035415 (2018)

Correlating electronic and magnetic coupling in large magnetic molecules via scanning tunneling microscopy In an effort to improve the spin coupling in single-molecule magnets, the authors rationally designed a new building-block molecule with significantly enhanced spin coupling compared to a previously established molecule. The authors relate this to a stabilization of aromaticity in the central connecting carbon ring, promoting the spin-polarization mechanism. This correlation between magnetic and electronic properties is supported by bulk measurements as well as submolecularly resolved scanning tunneling microscopy and spectroscopy experiments, where the authors found distinct differences in the local density of states distribution of the two molecules, especially at the central carbon ring. While the established molecule exhibits localized, spatially decoupled and even switchable states, the improved building block exhibits symmetric local density of states delocalized over the entire molecule, also revealing that this main characteristic electronic property is preserved upon adsorption on a metal surface. Due to their planar geometry, these molecules can serve as model systems for scanning-probe based studies of molecular magnetism. Judith Donner, Jan-Philipp Broschinski, Bastian Feldscher, Anja Stammler, Hartmut Bögge, Thorsten Glaser, Daniel Wegner, Correlating electronic and magnetic coupling in large magnetic molecules via scanning tunneling microscopy, Phys. Rev. B 95, 165441 (2017)

The Mn12-story goes on The discovery of magnetic bistability in Mn12 more than 20 years ago marked the birth of molecular magnetism, an extremely fertile interdisciplinary field and a powerful route to create tailored magnetic nanostructures. However, the difficulty to determine interactions in complex polycentric molecules often prevents their understanding. Mn12 is an outstanding example of this difficulty: although it is the forefather and most studied of all molecular nanomagnets, an unambiguous determination of even the leading magnetic exchange interactions is still lacking. Here the authors exploit four-dimensional inelastic neutron scattering to portray how individual spins fluctuate around the magnetic ground state, thus fixing the exchange couplings of Mn12 for the first time. The results demonstrate the power of four-dimensional inelastic neutron scattering as an unrivaled tool to characterize magnetic clusters. A. Chiesa, T. Guidi, S. Carretta, S. Ansbro, G.A. Timco, I. Vitorica-Yrezabal, E. Garlatti, G. Amoretti, R.E.P. Winpenny, and P. Santini, Magnetic Exchange Interactions in the Molecular Nanomagnet Mn12, Phys. Rev. Lett. 119, 217202 (2017)

Operating Quantum States in Single Magnetic Molecules: Implementation of Grover's Quantum Algorithm Quantum algorithms use the principles of quantum mechanics, such as, for example, quantum superposition, in order to solve particular problems outperforming standard computation. They are developed for cryptography, searching, optimization, simulation, and solving large systems of linear equations. In this publication the authors implement Grover's quantum algorithm, proposed to find an element in an unsorted list, using a single nuclear spin 3/2 carried by a Tb ion sitting in a single molecular magnet transistor. The coherent manipulation of this multilevel quantum system (qudit) is achieved by means of electric fields only. Grover's search algorithm is implemented by constructing a quantum database via a multilevel Hadamard gate. The Grover sequence then allows us to select each state. The presented method is of universal character and can be implemented in any multilevel quantum system with nonequal spaced energy levels, opening the way to novel quantum search algorithms. C. Godfrin, A. Ferhat, R. Ballou, S. Klyatskaya, M. Ruben, W. Wernsdorfer, and F. Balestro, Operating Quantum States in Single Magnetic Molecules: Implementation of Grover's Quantum Algorithm, Phys. Rev. Lett. 119, 187702

Topological Self-Assembly of Highly-Symmetric Lanthanide Clusters: A Magnetic Study of Exchange-Coupling "Fingerprints" in Giant Gadolinium(III) Cages The creation of a perfect hollow nanoscopic sphere of metal centres is clearly an unrealisable synthetic challenge. It is however an inspirational challenge, from the viewpoint of chemical architecture and also as finite molecular species may provide unique microscopic insight into the origin and onset of phenomena such as topological spin-frustration effects found in infinite 2D and 3D systems. Herein, we report a series of high symmetry gadolinium(III) (S = 7/2) polyhedra, Gd20, Gd32, Gd50 and Gd60, to test an approach based on assembling polymetallic fragments that contain different polygons. Structural analysis reveals the Gd20 cage resembles a dodecahedron; the vertices of the Gd32 polyhedron exactly reveal symmetry Oh; Gd50 displays an unprecedented polyhedron in which an icosidodecahedron Gd30 core is encapsulated by an outer Gd20 dodecahedral shell with approximate Ih symmetry; and the Gd60 shows a truncated octahedron geometry. Experimental and theoretical magnetic studies show that this series produces the expected antiferromagnetic interaction that can be modelled based on classical spins at the Gd sites. From the magnetization analyses we can roughly correlate the derivative bands to the Gd-O-Gd angles. Such a magneto-structural correlation may be used as "fingerprints" to identify these cages. Lei Qin, Guo-Jun Zhou, You-Zhu Yu, Hiroyuki Nojiri, Christian Schröder, Richard E. P. Winpenny, and Yan-Zhen Zheng, Topological Self-Assembly of Highly-Symmetric Lanthanide Clusters: A Magnetic Study of Exchange-Coupling "Fingerprints" in Giant Gadolinium(III) Cages, J. Am. Chem. Soc. 139, 16405 (2017)

Molecular magnetic hysteresis at 60 Kelvin in dysprosocenium Lanthanides have been investigated extensively for potential applications in quantum information processing and high-density data storage at the molecular and atomic scale. Experimental achievements include reading and manipulating single nuclear spins, exploiting atomic clock transitions for robust qubits and, most recently, magnetic data storage in single atoms. Single-molecule magnets exhibit magnetic hysteresis of molecular origin - a magnetic memory effect and a prerequisite of data storage - and so far lanthanide examples have exhibited this phenomenon at the highest temperatures. However, in the nearly 25 years since the discovery of single-molecule magnets, hysteresis temperatures have increased from 4 Kelvin to only about 14 Kelvin using a consistent magnetic field sweep rate of about 20 oersted per second, although higher temperatures have been achieved by using very fast sweep rates (for example, 30 Kelvin with 200 oersted per second). Here the authors report a hexa-tert-butyldysprosocenium complex which exhibits magnetic hysteresis at temperatures of up to 60 Kelvin at a sweep rate of 22 oersted per second. We observe a clear change in the relaxation dynamics at this temperature, which persists in magnetically diluted samples, suggesting that the origin of the hysteresis is the localized metal-ligand vibrational modes that are unique to dysprosocenium. Ab initio calculations of spin dynamics demonstrate that magnetic relaxation at high temperatures is due to local molecular vibrations. These results indicate that, with judicious molecular design, magnetic data storage in single molecules at temperatures above liquid nitrogen should be possible. Conrad A. P. Goodwin, Fabrizio Ortu, Daniel Reta, Nicholas F. Chilton, David P. Mills, Molecular magnetic hysteresis at 60 Kelvin in dysprosocenium, Nature 548, 439-442 (2017) Roberta Sessoli, Materials science: Magnetic molecules back in the race, Nature 548, 400-401 (2017)

Narrowing the Zero-Field Tunneling Resonance by Decreasing the Crystal Symmetry of Mn12 Acetate The authors report the discovery of a less symmetric crystalline phase of Mn12 acetate, a triclinic phase, resulting from recrystallizing the original tetragonal phase reported by Lis in acetonitrile and toluene. This new phase exhibits the same structure of Mn12 acetate clusters and the same positions of tunneling resonances on the magnetic field as the conventional tetragonal phase. However, the width of the zero-field resonance is at least 1 order of magnitude smaller, can be as low as 50 Oe, indicating very small inhomogeneous broadening due to dipolar and nuclear fields. Jordi Espin, Ricardo Zarzuela, Nahuel Statuto, Jordi Juanhuix, Daniel Maspoch, Inhar Imaz, Eugene Chudnovsky, Javier Tejada, Narrowing the Zero-Field Tunneling Resonance by Decreasing the Crystal Symmetry of Mn12 Acetate, J. Am. Chem. Soc., 2016, 138, 9065-9068

Put the spin in a cage To increase the temperature at which molecules behave as single-molecule magnets (SMM) is a serious challenge in molecular magnetism. One of the ways to address this problem is to create molecules with strongly coupled lanthanide ions. In the presented work, endohedral metallofullerenes Y2@C80 and Dy2@C80 are obtained in the form of air-stable benzyl monoadducts. Both feature an unpaired electron trapped between metal ions, thus forming a single-electron metal-metal bond. Giant exchange interactions between lanthanide ions and the unpaired electron result in single-molecule magnetism of Dy2@C80(CH2Ph) with a record-high 100 seconds blocking temperature of 18 K. All magnetic moments in Dy2@C80(CH2Ph) are parallel and couple ferromagnetically to form a single spin unit of 21 Bohr magnetons with a dysprosium-electron exchange constant of 32 cm-1. The barrier of the magnetization reversal of 613 K is assigned to the state in which the spin of one Dy centre is flipped. Fupin Liu, Denis S. Krylov, Lukas Spree, Stanislav M. Avdoshenko, Nataliya A. Samoylova, Marco Rosenkranz, Aram Kostanyan, Thomas Greber, Anja U. B. Wolter, Bernd Büchner, Alexey A. Popov, Single molecule magnet with an unpaired electron trapped between two lanthanide ions inside a fullerene, Nature Communications 8, 16098 (2017) D. S. Krylov, F. Liu, S. M. Avdoshenko, L. Spree, B. Weise, A. Waske, A. U. B. Wolter, B. Büchner, A. A. Popov, Record-high thermal barrier of the relaxation of magnetization in the nitride clusterfullerene Dy2ScN@C80-Ih, Chem. Commun., 2017, 53, 7901-7904

A microscopic refrigeration process triggered through spin-crossover mechanism The author reports the giant barocaloric effect determined in a spin-crossover system using a microscopic model. Compared with the widely used gas compression-expansion refrigeration technology, field induced refrigeration in solid materials reduces environmental damages and improves the energy efficiency. The origin of the giant effect was ascribed to the entropic phonon contribution arising from low spin to high spin phase transition, induced by a pressure change. Here, the author shows that for the applied pressure variation from 1 bar to 4.1 kbar, the isothermal entropy change in a one-dimensional spin crossover system [Fe(hyptrz)3](4-chlorophenylsulfonate)2H2O achieves a maximum value of 55.8 J/(mol K) at 191 K, leading to a huge refrigerant capacity of 2160 J/mol. The results were compared with the results of other giant solid refrigerant materials such as (NH4)2SO4, Gd5Si2Ge2, and Gd5[Si0.43Ge0.57]4. The potential of a solid refrigerant material is characterized by the isothermal entropy change upon controlled external field variations. If this quantity is obtained upon magnetic field variations, a magnetocaloric effect occurs; upon an electrical field change or a pressure change, electrocaloric or barocaloric effects occur, respectively. P. J. von Ranke, A microscopic refrigeration process triggered through spin-crossover mechanism, Appl. Phys. Lett. 110, 181909 (2017)

Recent progress in synchrotron-based frequency-domain Fourier-transform THz-EPR We describe frequency-domain Fourier-transform THz-EPR as a method to assign spin-coupling parameters of high-spin (S > 1/2) systems with very large zero-field splittings. The instrumental foundations of synchrotron-based FD-FT THz-EPR are presented, alongside with a discussion of frequency-domain EPR simulation routines. The capabilities of this approach is demonstrated for selected mono- and multinuclear HS systems. Finally, we discuss remaining challenges and give an outlook on the future prospects of the technique. Joscha Nehrkorn, Karsten Holldack, Robert Bittl, Alexander Schnegg, Recent progress in synchrotron-based frequency-domain Fourier-transform THz-EPR, Journal of Magnetic Resonance 280, 10-19 2017

Long-range ferrimagnetic order in a two-dimensional supramolecular Kondo lattice Realization of long-range magnetic order in surface-supported two-dimensional systems has been challenging, mainly due to the competition between fundamental magnetic interactions as the short-range Kondo effect and spin-stabilizing magnetic exchange interactions. Spin-bearing molecules on conducting substrates represent a rich platform to investigate the interplay of these fundamental magnetic interactions. Here we demonstrate the direct observation of long-range ferrimagnetic order emerging in a two-dimensional supramolecular Kondo lattice. The lattice consists of paramagnetic hexadeca-fluorinated iron phthalocyanine (FeFPc) and manganese phthalocyanine (MnPc) molecules co-assembled into a checkerboard pattern on single-crystalline Au(111) substrates. Remarkably, the remanent magnetic moments are oriented in the out-of-plane direction with significant contribution from orbital moments. First-principles calculations reveal that the FeFPc-MnPc antiferromagnetic nearest-neighbour coupling is mediated by the Ruderman-Kittel-Kasuya-Yosida exchange interaction via the Au substrate electronic states. Our findings suggest the use of molecular frameworks to engineer novel low-dimensional magnetically ordered materials and their application in molecular quantum devices. Jan Girovsky, Jan Nowakowski, Md. Ehesan Ali, Milos Baljozovic, Harald R. Rossmann, Thomas Nijs, Elise A. Aeby, Sylwia Nowakowska, Dorota Siewert, Gitika Srivastava, Christian Wäckerlin, Jan Dreiser, Silvio Decurtins, Shi-Xia Liu, Peter M. Oppeneer, Thomas A. Jung, Nirmalya Ballav, Long-range ferrimagnetic order in a two-dimensional supramolecular Kondo lattice, Nature Communications 8, 15388 (2017)

A chimeric design of heterospin 2p-3d, 2p-4f, and 2p-3d-4f complexes using a novel family of paramagnetic dissymmetric compartmental ligands End-off bicompartmental ligands bearing a nitronyl-nitroxide arm have been designed for synthesizing various heterospin molecular systems. These ligands can selectively interact with 3d and 4f metal ions, leading to 2p-4f, 2p-3d, and 2p-3d-4f complexes. The magnetic properties of the 2p-4f and 2p-3d-4f complexes have been investigated and rationalized by theoretical calculations. Andrei A. Patrascu, Sergiu Calancea, Matteo Briganti, Stephane Soriano, Augustin M. Madalan, Rafael A. Allao Cassaro, Andrea Caneschi, Federico Totti, Maria G. F. Vaz and Marius Andruh, A chimeric design of heterospin 2p-3d, 2p-4f, and 2p-3d-4f complexes using a novel family of paramagnetic dissymmetric compartmental ligands, Chem. Commun., 2017, 53, 6504

Portraying entanglement between molecular qubits with four-dimensional inelastic neutron scattering Entanglement is a crucial resource for quantum information processing and its detection and quantification is of paramount importance in many areas of current research. Weakly coupled molecular nanomagnets provide an ideal test bed for investigating entanglement between complex spin systems. However, entanglement in these systems has only been experimentally demonstrated rather indirectly by macroscopic techniques or by fitting trial model Hamiltonians to experimental data. Here the authors show that four-dimensional inelastic neutron scattering enables one to portray entanglement in weakly coupled molecular qubits and to quantify it. To this end a prototype (Cr7Ni)2 supramolecular dimer is exploited as a benchmark to demonstrate the potential of this approach, which allows one to extract the concurrence in eigenstates of a dimer of molecular qubits without diagonalizing its full Hamiltonian. E. Garlatti, T. Guidi, S. Ansbro, P. Santini, G. Amoretti, J. Ollivier, H. Mutka, G. Timco, I.J. Vitorica-Yrezabal, G.F.S. Whitehead, R.E.P. Winpenny, S. Carretta, Portraying entanglement between molecular qubits with four-dimensional inelastic neutron scattering, Nature Communications 8, 14543 (2017)

Molecular magnetism, quo vadis? A historical perspective from a coordination chemist viewpoint Molecular magnetism has travelled a long way from the pioneering studies on electron exchange and double exchange or spin crossover and valence tautomerism in small oligonuclear complexes, from mono- to di- and tetranuclear species, to the current investigations about magnetic anisotropy and spin dynamics or quantum coherence of simple mono- or large polynuclear complexes, behaving as switchable bistable molecular nanomagnets for potential applications in information data storage and processing. In this review, the authors focus on the origin and development of the research in the field of molecular magnetism from a coordination chemistry viewpoint, which dates back to the establishment of magnetochemistry as a novel discipline among the molecular sciences. This overview is conceived as an attempt to orientate coordination chemists regarding their role in the future direction that molecular magnetism will undergo in its further evolution toward molecular spintronics and quantum computation. A particular emphasis will be given to some selected recent advances in single-molecule spintronic circuitry and quantum computing devices based on the large class of multiresponsive and multifunctional magnetic metal complexes to stimulate the progress in the field of molecular magnetism. Jesús Ferrando-Soria, Julia Vallejo, María Castellano, José Martínez-Lillo, Emilio Pardo, Joan Cano, Isabel Castro, Francesc Lloret, Rafael Ruiz-García, Miguel Julve, Molecular magnetism, quo vadis? A historical perspective from a coordination chemist viewpoint, Coordination Chemistry Reviews 339 (2017) 17-103

Room Temperature Magnetoresistance in Single-Molecule Devices Two recent publications show that the appropriate choice of the transition metal complex and metal surface electronic structure opens the possibility to control the spin of the charge carriers through the resulting hybrid molecule/metal spinterface in a single-molecule electrical contact at room temperature. Albert C. Aragones, Daniel Aravena, Francisco J. Valverde-Munoz, Jose Antonio Real, Fausto Sanz, Ismael Diez-Perez, Eliseo Ruiz, Metal-Controlled Magnetoresistance at Room Temperature in Single-Molecule Devices, J. Am. Chem. Soc., 2017, 139 (16), pp 5768-5778 Albert C. Aragones, Daniel Aravena, Jorge I. Cerda, Zulema Acis-Castillo, Haipeng Li, Jose Antonio Real, Fausto Sanz, Josh Hihath, Eliseo Ruiz, Ismael Diez-Perez, Large Conductance Switching in a Single-Molecule Device through Room Temperature Spin-Dependent Transport, Nano Lett., 2016, 16 (1), pp 218-226

Recent Development in Clusters of Rare Earths and Actinides: Chemistry and Materials With contributions by Zhonghao Zhang, Yanan Zhang, Zhiping Zheng, Xiu-Ying Zheng, Xiang-Jian Kong, La-Sheng Long, Jian-Wen Cheng, Guo-Yu Yang, Sarah Hickam, Peter C. Burns, Xiaoping Yang, Shiqing Wang, Chengri Wang, Shaoming Huang, Richard A. Jones, Yan-Cong Chen, Jun-Liang Liu, Ming-Liang Tong, Tian Han, You-Song Ding, Yan-Zhen Zheng, Takanori Shima, Zhaomin Hou Recent Development in Clusters of Rare Earths and Actinides: Chemistry and Materials, Editors: Zhiping Zheng, Structure and Bonding, Volume 173 2017Springer, ISBN: 978-3-662-53301-7 (Print) 978-3-662-53303-1 (Online), online

Spin Dynamics and Low Energy Vibrations: Insights from Vanadyl-Based Potential Molecular Qubits In this communication the authors report the investigation of the magnetization dynamics of a vanadyl complex with diethyldithiocarbamate (Et2dtc-) ligands in both solid-state and frozen solution. The investigation showed an anomalous and unprecedentedly observed field dependence of the relaxation time, which was modeled with three contributions to the relaxation mechanism. The temperature dependence of the weight of the two processes dominating at low fields was found to well correlate with the low energy vibrations as determined by THz spectroscopy. This detailed experimental comparative study represents a fundamental step to understand the spin dynamics of potential molecular quantum bits and enriches the guidelines to design molecule-based systems with enhanced quantum coherence. Matteo Atzori, Lorenzo Tesi, Stefano Benci, Alessandro Lunghi, Roberto Righini, Andrea Taschin, Renato Torre, Lorenzo Sorace, Roberta Sessoli, Spin Dynamics and Low Energy Vibrations: Insights from Vanadyl-Based Potential Molecular Qubits, J. Am. Chem. Soc., 2017, 139 (12), pp 4338-4341

The role of anharmonic phonons in under-barrier spin relaxation of single molecule magnets The use of single molecule magnets in mainstream electronics requires their magnetic moment to be stable over long times. One can achieve such a goal by designing compounds with spin-reversal barriers exceeding room temperature, namely with large uniaxial anisotropies. Such strategy, however, has been defeated by several recent experiments demonstrating under-barrier relaxation at high temperature, a behaviour today unexplained. Here the authors propose spin-phonon coupling to be responsible for such anomaly. With a combination of electronic structure theory and master equations the authors show that, in the presence of phonon dissipation, the relevant energy scale for the spin relaxation is given by the lower-lying phonon modes interacting with the local spins. These open a channel for spin reversal at energies lower than that set by the magnetic anisotropy, producing fast under-barrier spin relaxation. The findings rationalize a significant body of experimental work and suggest a possible strategy for engineering room temperature single molecule magnets. Alessandro Lunghi, Federico Totti, Roberta Sessoli, Stefano Sanvito, The role of anharmonic phonons in under-barrier spin relaxation of single molecule magnets, Nature Communications 8, 14620 (2017)

Pressure induced enhancement of the magnetic ordering temperature in rhenium(IV) monomers Materials that demonstrate long-range magnetic order are synonymous with information storage and the electronics industry, with the phenomenon commonly associated with metals, metal alloys or metal oxides and sulfides. A lesser known family of magnetically ordered complexes are the monometallic compounds of highly anisotropic d-block transition metals; the 'transformation' from isolated zero-dimensional molecule to ordered, spin-canted, three-dimensional lattice being the result of through-space interactions arising from the combination of large magnetic anisotropy and spin-delocalization from metal to ligand which induces important intermolecular contacts. Here the authors report the effect of pressure on two such mononuclear rhenium(IV) compounds that exhibit long-range magnetic order under ambient conditions via a spin canting mechanism, with Tc controlled by the strength of the intermolecular interactions. As these are determined by intermolecular distance, 'squeezing' the molecules closer together generates remarkable enhancements in ordering temperatures, with a linear dependence of Tc with pressure. Christopher H. Woodall, Gavin A. Craig, Alessandro Prescimone, Martin Misek, Joan Cano, Juan Faus, Michael R. Probert, Simon Parsons, Stephen Moggach, Jose Martinez-Lillo, Mark Murrie, Konstantin V. Kamenev, Euan K. Brechin, Pressure induced enhancement of the magnetic ordering temperature in rhenium(IV) monomers, Nature Communications 7, 13870 (2016)

Precision ESR measurements of transverse anisotropy in the single-molecule magnet Ni4 The authors present a method for precisely measuring the tunnel splitting in single-molecule magnets (SMMs) using electron-spin resonance, and use these measurements to precisely and independently determine the underlying transverse anisotropy parameter, given a certain class of transitions. By diluting samples of the SMM Ni4 via cocrystallization in a diamagnetic isostructural analog we obtain markedly narrower resonance peaks than are observed in undiluted samples. Using custom loop-gap resonators we measure the transitions at several frequencies, allowing a precise determination of the tunnel splitting. Because the transition under investigation occurs at zero field, and arises due to a first-order perturbation from the transverse anisotropy, we can determine the magnitude of this anisotropy independent of any other Hamiltonian parameters. This method can be applied to other SMMs with tunnel splittings arising from first-order transverse anisotropy perturbations. Charles A. Collett, Rafael A. Allao Cassaro, and Jonathan R. Friedman, Precision ESR measurements of transverse anisotropy in the single-molecule magnet Ni4, Phys. Rev. B 94, 220402(R) (2016)

First cage-like pentanuclear Co(II)-silsesquioxane A new pentanuclear cylinder-like cobalt(II) phenylsilsesquioxane exhibits a slow relaxation of the magnetization and a high catalytic activity and stereoselectivity in the oxidation of alkanes and alcohols. A. N. Bilyachenko, A. I. Yalymov, M. M. Levitsky, A. A. Korlyukov, M. A. Es'kova, J. Long, J. Larionova, Y. Guari, L. S. Shul'pina, N. S. Ikonnikov, A. L. Trigub, Y. V. Zubavichus, I. E. Golub, E. S. Shubina and G. B. Shul'pin, First cage-like pentanuclear Co(II)-silsesquioxane, Dalton Trans., 2016,45, 13663-13666

Molecular Magnetic Materials: Concepts and Applications A comprehensive overview of this rapidly expanding interdisciplinary field of research. After a short introduction to the basics of magnetism and molecular magnetism, the text goes on to cover specific properties of molecular magnetic materials as well as their current and future applications. Design strategies for acquiring molecular magnetic materials with desired physical properties are discussed, as are such multifunctional materials as high Tc magnets, chiral and luminescent magnets, magnetic sponges as well as photo- and piezo-switching magnets. The result is an excellent resource for materials scientists, chemists, physicists and crystal engineers either entering or already working in the field. With contributions of: Maria Balanda, Robert Pelka, Michael Shatruk, Silvia Gomez-Coca, Kim R. Dunbar, Zhao-Ping Ni, Ming-Liang Tong, Masahiro Yamashita, Keiichi Katoh, Paolo Santini, Stefano Carretta, Giuseppe Amoretti, Kasper S. Pedersen, Alessandro Vindigni, Roberta Sessoli, Claude Coulon, Rodolphe Clerac, Joel S. Miller, Shin-ichi Ohkoshi, Andrea Cornia, Daniel R. Talham, Marco Affronte, Ana B. Gaspar, Birgit Weber, Wei-Xiong Zhang, Ming-Hua Zeng, Xiao-Ming Chen, Dawid Pinkowicz, Robet Podgajny, Barbara Sieklucka, Cyrille Train, Geert Rikken, Michel Verdaguer, Corine Mathoniere, Hiroko Tokoro, Shin-ichi Ohkoshi , Mauro Perfetti, Fabrice Pointillart, Olivier Cador, Lorenzo Sorace, Lahcene Ouahab, Yoshihiro Sekine, Wataru Kosaka, Kouji Taniguchi, Hitoshi Miyasaka, Thomas T. M. Palstra, Alexey O. Polyakov, Jordi Cirera, Eliseo Ruiz, Jürgen Schnack and Coen de Graaf. Barbara Sieklucka (Editor), Dawid Pinkowicz (Editor), Molecular Magnetic Materials: Concepts and Applications, WILEY, 2016, ISBN: 978-3-527-33953-2

On Approaching the Limit of Molecular Magnetic Anisotropy: A Near-Perfect Pentagonal Bipyramidal Dysprosium(III) Single-Molecule Magnet The authos report a monometallic dysprosium complex, that shows the largest effective energy barrier to magnetic relaxation of Ueff=1815 K. The massive magnetic anisotropy is due to bis-trans-disposed tert-butoxide ligands with weak equatorial pyridine donors, approaching proposed schemes for high-temperature single-molecule magnets (SMMs). The blocking temperature is 14 K, defined by zero-field-cooled magnetization experiments, and is the largest for any monometallic complex. You-Song Ding, Nicholas F. Chilton, Richard E. P. Winpenny, Yan-Zhen Zheng, On Approaching the Limit of Molecular Magnetic Anisotropy: A Near-Perfect Pentagonal Bipyramidal Dysprosium(III) Single-Molecule Magnet, Angew. Chem. Int. Ed. 55, 16071 (2016)

Research Update: The mechanocaloric potential of spin crossover compounds The author presents a first evaluation of the potential for spin crossover (SCO) compounds to be considered as a new class of giant mechanocaloric effect materials. From literature data on the variation of the spin crossover temperature with pressure, we estimate the maximum available adiabatic temperature change for several compounds and the relatively low pressures that may be required to observe these effects. Karl G. Sandeman, Research Update: The mechanocaloric potential of spin crossover compounds, APL Mater. 4, 111102 (2016)

Observation of Tunneling-Assisted Highly Forbidden Single-Photon Transitions in a Ni4 Single-Molecule Magnet Forbidden transitions between energy levels typically involve violation of selection rules imposed by symmetry and/or conservation laws. A nanomagnet tunneling between up and down states violates angular momentum conservation because of broken rotational symmetry. Here the authors report observations of highly forbidden transitions between spin states in a Ni4 single-molecule magnet in which a single photon can induce the spin to change by several times hbar, nearly reversing the direction of the spin. These observations are understood as tunneling-assisted transitions that lift the standard Delta m=+/-1 selection rule for single-photon transitions. These transitions are observed at low applied fields, where tunneling is dominated by the molecule's intrinsic anisotropy and the field acts as a perturbation. Such transitions can be exploited to create macroscopic superposition states that are not typically accessible through single-photon Delta m=+/-1 transitions. Yiming Chen, Mohammad D. Ashkezari, Charles A. Collett, Rafael A. Allao Cassaro, Filippo Troiani, Paul M. Lahti, and Jonathan R. Friedman, Observation of Tunneling-Assisted Highly Forbidden Single-Photon Transitions in a Ni4 Single-Molecule Magnet, Phys. Rev. Lett. 117, 187202 (2016)

Experimental and theoretical investigation of the magnetization dynamics of an artificial square spin ice cluster The authors study the magnetization dynamics of a spin ice cluster which is a building block of an artificial square spin ice fabricated by focused electron-beam-induced deposition both experimentally and theoretically. The spin ice cluster is composed of twelve interacting Co nanoislands grown directly on top of a high-resolution micro-Hall sensor. By employing micromagnetic simulations and a macrospin model, we calculate the magnetization and the experimentally investigated stray field emanating from a single nanoisland. The parameters determined from a comparison with the experimental hysteresis loop are used to derive an effective single-dipole macrospin model that allows us to investigate the dynamics of the spin ice cluster. Our model reproduces the experimentally observed non-deterministic sequences in the magnetization curves as well as the distinct temperature dependence of the hysteresis loop. Merlin Pohlit, Irina Stockem, Fabrizio Porrati, Michael Huth, Christian Schröder and Jens Müller, Experimental and theoretical investigation of the magnetization dynamics of an artificial square spin ice cluster, J. Appl. Phys. 120, 142103 (2016)

Understanding Thermodynamic and Spectroscopic Properties of Tetragonal Mn12 Single-Molecule Magnets from Combined Density Functional Theory/Spin-Hamiltonian Calculations The authors apply broken-symmetry density functional theory to determine isotropic exchange-coupling constants and local zero-field splitting (ZFS) tensors for the tetragonal Mn12tBuAc single-molecule magnet. The obtained parametrization of the many-spin Hamiltonian (MSH), taking into account all 12 spin centers, is assessed by comparing theoretical predictions for thermodynamic and spectroscopic properties with available experimental data. The magnetic susceptibility (calculated by the finite-temperature Lanczos method) is well approximated, and the intermultiplet excitation spectrum from inelastic neutron scattering (INS) experiments is correctly reproduced. In these respects, the present parametrization of the 12-spin model represents a significant improvement over previous theoretical estimates of exchange-coupling constants in Mn12, and additionally offers a refined interpretation of INS spectra. Treating anisotropic interactions at the third order of perturbation theory, the MSH is mapped onto the giant-spin Hamiltonian describing the S = 10 ground multiplet. Although the agreement with high-field EPR experiments is not perfect, the results clearly point in the right direction and for the first time rationalize the angular dependence of the transverse-field spectra from a fully microscopic viewpoint. Importantly, transverse anisotropy of the effective S = 10 manifold is explicitly shown to arise largely from the ZFS-induced mixing of exchange multiplets. This effect is given a thorough analysis in the approximate D2d spin-permutational symmetry group of the exchange Hamiltonian. Shadan Ghassemi Tabrizi, Alexei V. Arbuznikov, and Martin Kaupp, Understanding Thermodynamic and Spectroscopic Properties of Tetragonal Mn12 Single-Molecule Magnets from Combined Density Functional Theory/Spin-Hamiltonian Calculations, J. Phys. Chem. A, 2016, 120 (34), pp 6864-6879

Electron paramagnetic resonance of individual atoms on a surface Electron paramagnetic resonance (EPR) usually detects atoms with unpaired electrons as ensemble averages. The authors employed a spin-polarized scanning tunneling microscope tip to measure EPR spectra of single iron atoms adsorbed on a magnesium oxide surface at cryogenic temperatures. The high-energy resolution of conventional spin resonance was combined with scanning tunneling microscopy to measure electron paramagnetic resonance of individual iron (Fe) atoms placed on a magnesium oxide film. The spin resonance was driven with an oscillating electric field between tip and sample. The readout of the Fe atom's quantum state was performed by spin-polarized detection of the atomic-scale tunneling magnetoresistance. T1 and T2 times were determined. The spin resonance signals of different Fe atoms differ by much more than their resonance linewidth; in a traditional ensemble measurement, this difference would appear as inhomogeneous broadening. Susanne Baumann, William Paul, Taeyoung Choi, Christopher P. Lutz, Arzhang Ardavan, Andreas J. Heinrich, Electron paramagnetic resonance of individual atoms on a surface, Science 23 Oct 2015, Vol. 350, Issue 6259, pp. 417-420

Quantum Einstein-de Haas effect The classical Einstein-de Haas experiment demonstrates that a change of magnetization in a macroscopic magnetic object results in a mechanical rotation of this magnet. This experiment can therefore be considered as a macroscopic manifestation of the conservation of total angular momentum and energy of electronic spins. Since the conservation of angular momentum is a consequence of a system's rotational invariance, it is valid for an ensemble of spins in a macroscopic ferromaget as well as for single spins. Here we propose an experimental realization of an Einstein-de Haas experiment at the single-spin level based on a single-molecule magnet coupled to a nanomechanical resonator. We demonstrate that the spin associated with the single-molecule magnet is then subject to conservation of total angular momentum and energy, which results in a total suppression of the molecule's quantum tunnelling of magnetization. Marc Ganzhorn, Svetlana Klyatskaya, Mario Ruben, Wolfgang Wernsdorfer, Quantum Einstein-de Haas effect, Nature Communications 7, 11443 (2016)

The classical and quantum dynamics of molecular spins on graphene Controlling the dynamics of spins on surfaces is pivotal to the design of spintronic and quantum computing devices. Proposed schemes involve the interaction of spins with graphene to enable surface-state spintronics and electrical spin manipulation. However, the influence of the graphene environment on the spin systems has yet to be unravelled. Here we explore the spin-graphene interaction by studying the classical and quantum dynamics of molecular magnets on graphene. Whereas the static spin response remains unaltered, the quantum spin dynamics and associated selection rules are profoundly modulated. The couplings to graphene phonons, to other spins, and to Dirac fermions are quantified using a newly developed model. Coupling to Dirac electrons introduces a dominant quantum relaxation channel that, by driving the spins over Villain's threshold, gives rise to fully coherent, resonant spin tunnelling. Our findings provide fundamental insight into the interaction between spins and graphene, establishing the basis for electrical spin manipulation in graphene nanodevices. Christian Cervetti, Angelo Rettori, Maria Gloria Pini, Andrea Cornia, Ana Repolles, Fernando Luis, Martin Dressel, Stephan Rauschenbach, Klaus Kern, Marko Burghard, Lapo Bogani, The classical and quantum dynamics of molecular spins on graphene, Nature Materials 15, 164-168 (2016)

Making hybrid [n]-rotaxanes as supramolecular arrays of molecular electron spin qubits Quantum information processing (QIP) would require that the individual units involved-qubits-communicate to other qubits while retaining their identity. In many ways this resembles the way supramolecular chemistry brings together individual molecules into interlocked structures, where the assembly has one identity but where the individual components are still recognizable. Here a fully modular supramolecular strategy has been to link hybrid organic-inorganic [2]- and [3]-rotaxanes into still larger [4]-, [5]- and [7]-rotaxanes. The ring components are heterometallic octanuclear Cr7Ni coordination cages and the thread components template the formation of the ring about the organic axle, and are further functionalized to act as a ligand, which leads to large supramolecular arrays of these heterometallic rings. As the rings have been proposed as qubits for QIP, the strategy provides a possible route towards scalable molecular electron spin devices for QIP. Double electron-electron resonance experiments demonstrate inter-qubit interactions suitable for mediating two-qubit quantum logic gates. Antonio Fernandez, Jesus Ferrando-Soria, Eufemio Moreno Pineda, Floriana Tuna, Inigo J. Vitorica-Yrezabal, Christiane Knappke, Jakub Ujma, Christopher A. Muryn, Grigore A. Timco, Perdita E. Barran, Arzhang Ardavan, Richard E.P. Winpenny, Making hybrid [n]-rotaxanes as supramolecular arrays of molecular electron spin qubits, NATURE COMMUNICATIONS 7, 10240 (2016)

Studies on the Magnetic Ground State of a Spin Möbius Strip The authors report the synthesis, structure and detailed characterisation of three n-membered oxovanadium rings. Their alternating heterometallic vanadium/sodium cyclic core structures were sandwiched between two CD moieties such that O-Na-O groups separated the neighbouring vanadyl ions. Antiferromagnetic interactions between the S=1/2 vanadyl ions led to S=0 ground states for the even-membered rings, but to two quasi-degenerate S=1/2 states for the spin-frustrated heptanuclear cluster. This is one of the rather rare examples of odd membered antiferromagnetic spin rings. Graham N. Newton, Norihisa Hoshino, Takuto Matsumoto, Takuya Shiga, Motohiro Nakano, Hiroyuki Nojiri, Wolfgang Wernsdorfer, Yuji Furukawa, and Hiroki Oshio, Studies on the Magnetic Ground State of a Spin Möbius Strip, Chemistry - A European Journal 22 (2016) 14205

Dynamical effects on the magnetic properties of dithiazolyl bistable materials The magnetic properties of molecule-based magnets are commonly rationalized by considering only a single nuclear configuration of the system under study (usually an X-ray crystal structure). Here, by means of a computational study, we compare the results obtained using such a static approach with those obtained by explicitly accounting for thermal fluctuations, and uncover the serious limitations of the static perspective when dealing with magnetic crystals whose radicals undergo wide-amplitude motions. As a proof of concept, these limitations are illustrated for the magnetically bistable 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA) material. For its high-temperature phase at 300 K, we show that nuclear dynamics induce large fluctuations in the magnetic exchange interactions (J) between spins (up to 1000% of the average value). These deviations result in a about 20% difference between the 300 K magnetic susceptibility computed by explicitly considering the nuclear dynamics and that computed using the X-ray structure, the former being in better agreement with the experimental data. The unveiled strong coupling between J interactions and intermolecular vibrations reveals that considering J as a constant value at a given temperature (as always done in molecular magnetism) leads to a flawed description of the magnetism of TTTA. Instead, the physically relevant concept in this case is the statistical distribution of J values. Sergi Vela, Merce Deumal, Motoyuki Shiga, Juan J. Novoa, Jordi Ribas-Arino, Dynamical effects on the magnetic properties of dithiazolyl bistable materials, Chem. Sci., 2015, 6, 2371-2381

Enhancing coherence in molecular spin qubits via atomic clock transitions Quantum computing is an emerging area within the information sciences revolving around the concept of quantum bits (qubits). A major obstacle is the extreme fragility of these qubits due to interactions with their environment that destroy their quantumness. This phenomenon, known as decoherence, is of fundamental interest. When dealing with spin qubits, the strongest source of decoherence is the magnetic dipolar interaction. In This publication the authors present a way of enhancing coherence in solid-state molecular spin qubits without resorting to extreme dilution. It is based on the design of molecular structures with crystal field ground states possessing large tunnelling gaps that give rise to optimal operating points, or atomic clock transitions, at which the quantum spin dynamics become protected against dipolar decoherence. This approach is illustrated with a holmium molecular nanomagnet in which long coherence times (up to 8.4 microseconds at 5 kelvin) are obtained at unusually high concentrations. Muhandis Shiddiq, Dorsa Komijani, Yan Duan, Alejandro Gaita-Arino, Eugenio Coronado, Stephen Hill, Enhancing coherence in molecular spin qubits via atomic clock transitions, Nature 531, 348-351 (2016)

A Mixed-Ligand Approach for a Gigantic and Hollow Heterometallic Cage {Ni64RE96} for Gas Separation and Magnetic Cooling Applications Nanosized aggregations of metal ions shielded by organic ligands possessing both exquisite structural aesthetics and intriguing properties are fundamentally interesting. Three isostructural gigantic transition-metal-rare-earth heterometallic coordination cages are reported, abbreviated as {Ni64RE96} (RE=Gd, Dy, and Y) and obtained by a mixed-ligand approach, each possessing a cuboidal framework made of 160 metal ions and a nanosized spherical cavity in the center. Along with the structural novelty, these hollow cages show highly selective adsorptions for CO2 over CH4 or N2 at ambient temperatures. Moreover, the gadolinium analogue exhibits large magnetocaloric effect at ultralow temperatures. Wei-Peng Chen, Pei-Qin Liao, Youzhu Yu, Zhiping Zheng, Xiao-Ming Chen, Yan-Zhen Zheng A Mixed-Ligand Approach for a Gigantic and Hollow Heterometallic Cage {Ni64RE96} for Gas Separation and Magnetic Cooling Applications, Angew. Chem. Int. Ed. 2016, 55, 9375-9379

Modelling spin Hamiltonian parameters of molecular nanomagnets Molecular nanomagnets encompass a wide range of coordination complexes possessing several potential applications. A formidable challenge in realizing these potential applications lies in controlling the magnetic properties of these clusters. Microscopic spin Hamiltonian (SH) parameters describe the magnetic properties of these clusters, and viable ways to control these SH parameters are highly desirable. Computational tools play a proactive role in this area, where SH parameters such as isotropic exchange interaction (J), anisotropic exchange interaction (Jx, Jy, Jz), double exchange interaction (B), zero-field splitting parameters (D, E) and g-tensors can be computed reliably using X-ray structures. In this feature article the authors have attempted to provide a holistic view of the modelling of these SH parameters of molecular magnets. The determination of J includes various class of molecules, from di- and polynuclear Mn complexes to the {3d-Gd}, {Gd-Gd} and {Gd-2p} class of complexes. The estimation of anisotropic exchange coupling includes the exchange between an isotropic metal ion and an orbitally degenerate 3d/4d/5d metal ion. The double-exchange section contains some illustrative examples of mixed valance systems, and the section on the estimation of zfs parameters covers some mononuclear transition metal complexes possessing very large axial zfs parameters. The section on the computation of g-anisotropy exclusively covers studies on mononuclear DyIII and ErIII single-ion magnets. The examples depicted in this article clearly illustrate that computational tools not only aid in interpreting and rationalizing the observed magnetic properties but possess the potential to predict new generation MNMs. Tulika Gupta, Gopalan Rajaraman, Modelling spin Hamiltonian parameters of molecular nanomagnets, Chem. Commun., 2016, 52, 8972-9008

A modular design of molecular qubits to implement universal quantum gates The physical implementation of quantum information processing relies on individual modules - qubits - and operations that modify such modules either individually or in groups, i.e. quantum gates. Two examples of gates that entangle pairs of qubits are the controlled NOT-gate (CNOT) gate, which flips the state of one qubit depending on the state of another, and the SQRT(iSWAP) gate that brings a two-qubit product state into a superposition involving partially swapping the qubit states. Here we show that through supramolecular chemistry a single simple module, molecular {Cr7Ni} rings, which act as the qubits, can be assembled into structures suitable for either the CNOT or SQRT(iSWAP) gate by choice of linker, and we characterize these structures by electron spin resonance spectroscopy. We introduce two schemes for implementing such gates with these supramolecular assemblies and perform detailed simulations, based on the measured parameters including decoherence, to demonstrate how the gates would operate. Jesus Ferrando-Soria, Eufemio Moreno Pineda, Alessandro Chiesa, Antonio Fernandez, Samantha A. Magee, Stefano Carretta, Paolo Santini, Inigo J. Vitorica-Yrezabal, Floriana Tuna, Grigore A. Timco, Eric J.L. McInnes & Richard E.P. Winpenny, A modular design of molecular qubits to implement universal quantum gates, NATURE COMMUNICATIONS | 7:11377 (2016) see also: Alessandro Chiesa, George F. S. Whitehead, Stefano Carretta, Laura Carthy, Grigore A. Timco, Simon J. Teat, Giuseppe Amoretti, Eva Pavarini, Richard E. P. Winpenny, Paolo Santini, Molecular nanomagnets with switchable coupling for quantum simulation, SCIENTIFIC REPORTS | 4:7423 (2014)

D5h makes the difference Two more SIMs with record energy barrier and record magnetic hysteresis temperature have been reported recently. Air-stable Dy(III) and Er(III) single-ion magnets (SIMs) with pseudo-D5h symmetry, where the Dy(III)-SIM exhibits a magnetization blocking (TB) up to 12 K, defined from the maxima of the zero-field cooled magnetization curve, with an anisotropy barrier (Ueff) as high as 735.4 K have been reported. The Dy(III)-SIM exhibits a magnetic hysteresis up to 12 K (30 K) with a large coercivity of ~0.9 T (~1.5 T) at a sweep rate of ~0.0018 T/s (0.02 T/s). These high values combined with persistent stability under ambient conditions, render this system as one of the best-characterized SIMs. Ab initio calculations have been used to establish the connection between the higher-order symmetry of the molecule and the quenching of quantum tunnelling of magnetization (QTM) effects. The relaxation of magnetization is observed via the second excited Kramers doublet owing to pseudo-high-order symmetry, which quenches the QTM. This study highlights fine-tuning of symmetry around the lanthanide ion to obtain new-generation SIMs and offers further scope for pushing the limits of Ueff and TB using this approach. Sandeep K. Gupta, Thayalan Rajeshkumar, Gopalan Rajaraman, Ramaswamy Murugavel, An air-stable Dy(III) single-ion magnet with high anisotropy barrier and blocking temperature, Chem. Sci., 2016, Advance Article Sandeep K. Gupta, Thayalan Rajeshkumar, Gopalan Rajaraman, Ramaswamy Murugavel, An unprecedented zero field neodymium(III) single-ion magnet based on a phosphonic diamide, Chem. Commun., 2016,52, 7168-7171

Symmetry-Supported Magnetic Blocking at 20 K in Pentagonal Bipyramidal Dy(III) Single-Ion Magnets Two SIMs with record energy barrier and record magnetic hysteresis temperature up to 20 K, respectively, in two pentagonal bipyramidal Dy(III) SIMs have been reported recently. Single-molecule magnets (SMMs) that can be trapped in one of the bistable magnetic states separated by an energy barrier are among the most promising candidates for high-density information storage, quantum processing, and spintronics. To date, a considerable series of achievements have been made. However, the presence of fast quantum tunnelling of magnetization (QTM) in most SMMs, especially in single-ion magnets (SIMs), provides a rapid relaxation route and often sets up a limit for the relaxation time. Here, we pursue the pentagonal bipyramidal symmetry to suppress the QTM. Magnetic characterizations reveal fascinating SMM properties with high energy barriers along with a record magnetic hysteresis temperature up to 20 K. These results, combined with the ab initio calculations, offer an illuminating insight into the vast possibility and potential of what the symmetry rules can achieve in molecular magnetism. Yan-Cong Chen, Jun-Liang Liu, Liviu Ungur, Jiang Liu, Quan-Wen Li, Long-Fei Wang, Zhao-Ping Ni, Liviu F. Chibotaru, Xiao-Ming Chen, and Ming-Liang Tong, Symmetry-Supported Magnetic Blocking at 20 K in Pentagonal Bipyramidal Dy(III) Single-Ion Magnets, J. Am. Chem. Soc., 2016, 138 (8), pp 2829-2837 Jiang Liu, Yan-Cong Chen, Jun-Liang Liu, Veacheslav Vieru, Liviu Ungur, Jian-Hua Jia, Liviu F. Chibotaru, Yanhua Lan, Wolfgang Wernsdorfer, Song Gao, Xiao-Ming Chen, and Ming-Liang Tong, A Stable Pentagonal Bipyramidal Dy(III) Single-Ion Magnet with a Record Magnetization Reversal Barrier over 1000 K, J. Am. Chem. Soc., 2016, 138 (16), pp 5441-5450

Giant Hysteresis of Single-Molecule Magnets Adsorbed on a Nonmagnetic Insulator It is demonstrated that TbPc2 single-molecule magnets adsorbed on a magnesium oxide tunnel barrier exhibit record magnetic remanence, record hysteresis opening, perfect out-of-plane alignment of the magnetic easy axes, and self-assembly into a well-ordered layer. Christian Wäckerlin, Fabio Donati, Aparajita Singha, Romana Baltic, Stefano Rusponi, Katharina Diller, Francois Patthey, Marina Pivetta, Yanhua Lan, Svetlana Klyatskaya, Mario Ruben, Harald Brune, Jan Dreiser, Giant Hysteresis of Single-Molecule Magnets Adsorbed on a Nonmagnetic Insulator, Adv. Mater. 28 (2016) 5195-5199

Deciphering the origin of giant magnetic anisotropy and fast quantum tunnelling in Rhenium(IV) single-molecule magnets Single-molecule magnets represent a promising route to achieve potential applications such as high-density information storage and spintronics devices. Among others, 4d/5d elements such as Re(IV) ion are found to exhibit very large magnetic anisotropy, and inclusion of this ion-aggregated clusters yields several attractive molecular magnets. Here, using ab intio calculations, the authors unravel the source of giant magnetic anisotropy associated with the Re(IV) ions by studying a series of mononuclear Re(IV) six coordinate complexes. The low-lying doublet states are found to be responsible for large magnetic anisotropy and the sign of the axial zero-field splitting parameter (D) can be categorically predicted based on the position of the ligand coordination. Large transverse anisotropy along with large hyperfine interactions opens up multiple relaxation channels leading to a fast quantum tunnelling of the magneti- zation (QTM) process. Enhancing the Re-ligand covalency is found to significantly quench the QTM process. Saurabh Kumar Singh, Gopalan Rajaraman, Deciphering the origin of giant magnetic anisotropy and fast quantum tunnelling in Rhenium(IV) single-molecule magnets, NATURE COMMUNICATIONS 7, 10669 (2016)

Rotating Magnetocaloric Effect in an Anisotropic Molecular Dimer In contrast to the mainstream research on molecular refrigerants that seeks magnetically isotropic molecules, we show that the magnetic anisotropy of dysprosium acetate tetrahydrate, can be efficiently used for cooling below liquid-helium temperature. This is attained by rotating aligned single-crystal samples in a constant applied magnetic field. The envisioned advantages are fast cooling cycles and potentially compact refrigerators. Dr. Giulia Lorusso, Dr. Olivier Roubeau, Dr. Marco Evangelisti Rotating Magnetocaloric Effect in an Anisotropic Molecular Dimer, Angew. Chem. Int. Ed. 55 (2016) 3360-3363

Theoretical Modeling of the Magnetic Behavior of Thiacalix[4]arene Tetranuclear MnII2GdIII2 and CoII2EuIII2 Complexes In view of a wide perspective of 3d-4f complexes in single-molecule magnetism, here we propose an explanation of the magnetic behavior of the two thiacalix[4]arene tetranuclear heterometallic complexes MnII2GdIII2 and CoII2EuIII2. The energy pattern of the MnII2GdIII2 complex evaluated in the framework of the isotropic exchange model exhibits a rotational band of the low-lying spin excitations within which the Lande intervals are affected by the biquadratic spin-spin interactions. The nonmonotonic temperature dependence of the Chi*T product observed for the MnII2GdIII2 complex is attributed to the competitive influence of the ferromagnetic Mn-Gd and antiferromagnetic Mn-Mn exchange interactions, the latter being stronger. The model for the CoII2EuIII2 complex includes uniaxial anisotropy of the seven-coordinate Co ions and an isotropic exchange interaction in the Co pair, while the Eu ions are diamagnetic in their ground states. Best-fit analysis of Chi*T versus T showed that the anisotropic contribution (arising from a large zero-field splitting in Co ions) dominates (weak-exchange limit) in the CoII2EuIII2. This complex is concluded to exhibit an easy plane of magnetization (arising from the Co pair). It is shown that the low-lying part of the spectrum can be described by a highly anisotropic effective spin-1/2 Hamiltonian that is deduced for the CoII2 pair in the weak-exchange limit. Sergey M. Aldoshin, Nataliya A. Sanina, Andrew V. Palii, Boris S. Tsukerblat, Theoretical Modeling of the Magnetic Behavior of Thiacalix[4]arene Tetranuclear MnII2GdIII2 and CoII2EuIII2 Complexes, Inorg. Chem. (2016) Article ASAP

Molecular Nanomagnets and Related Phenomena With contributions by M. Affronte, M.L. Baker, S.J. Blundell, L. Bogani, L.F. Chibotaru, R. Clerac, A. Cornia, C. Coulon, N. Domingo, M. Evangelisti, S. Gao, A. Ghirri, S. Hill, S.-D. Jiang, F. Luis, M. Mannini, C.J. Milios, V. Pianet, F. Troiani, M. Urdampilleta, R.E.P. Winpenny, B.-W. Wang, Song Gao (Ed.), Molecular Nanomagnets and Related Phenomena, Structure and Bonding 164 (2015)

New single-ion magnets Single-molecule magnets display magnetic bistability of molecular origin, which may one day be exploited in magnetic data storage devices. Recently it was realised that increasing the magnetic moment of polynuclear molecules does not automatically lead to a substantial increase in magnetic bistability. Attention has thus increasingly focussed on ions with large magnetic anisotropies. In spite of large effective energy barriers towards relaxation of the magnetic moment, this has so far not led to a big increase in magnetic bistability. Here we present a comprehensive study of a mononuclear, tetrahedrally coordinated cobalt(II) single-molecule magnet, which has a very high effective energy barrier and displays pronounced magnetic bistability. The combined experimental-theoretical approach enables an in-depth understanding of the origin of these favourable properties, which are shown to arise from a strong ligand field in combination with axial distortion. Our findings allow formulation of clear design principles for improved materials. Yvonne Rechkemmer, Frauke D. Breitgoff, Margarethe van der Meer, Mihail Atanasov, Michael Hakl, Milan Orlita, Petr Neugebauer, Frank Neese, Biprajit Sarkar, Joris van Slageren A four-coordinate cobalt(II) single-ion magnet with coercivity and a very high energy barrier, Nature Communications 7, 10467 (2016) More on single-ion magnets: Yvonne Rechkemmer, Julia E. Fischer, Raphael Marx, Mari�a Dörfel, Petr Neugebauer, Sebastian Horvath, Maren Gysler, Theis Brock-Nannestad, Wolfgang Frey, Michael F. Reid, Joris van Slageren, Comprehensive Spectroscopic Determination of the Crystal Field Splitting in an Erbium Single-Ion Magnet, JACS 137, 13114 (2015)

Supramolecular aggregates of single-molecule magnets: exchange-biased quantum tunneling of magnetization in a rectangular [Mn3]4 tetramer The syntheses and properties of four magnetically-supramolecular oligomers of triangular Mn3 units are reported. Magnetization vs. dc field sweeps on a single crystal of the tetrameric [Mn12O4(O2CR)12(pdpd)6](ClO4)4 (R = Me) gave hysteresis loops below 1 K that exhibit exchange-biased quantum tunneling of magnetization (QTM) steps with a bias field of 0.19 T. Simulation of the loops determined that each Mn3 unit is exchange-coupled to the two neighbors. The work demonstrates a rational approach to synthesizing magnetically-supramolecular aggregates of SMMs as potential multi-qubit systems for quantum computing. Tu N. Nguyen, Wolfgang Wernsdorfer, Muhandis Shiddiq, Khalil A. Abboud, Stephen Hill, George Christou, Supramolecular aggregates of single-molecule magnets: exchange-biased quantum tunneling of magnetization in a rectangular [Mn3]4 tetramer, Chem. Sci. 7, 1156 (2016)

Thematic Issue: Phase Transition and Dynamical Properties of Spin Transition Materials Great attention in the area of spin transition materials has been paid to the investigation of their various phase transitions and dynamical properties which can be modulated by external parameters, including temperature, pressure, photo-irradiation, or presence of guest molecules. The topics collected in the issue are focused on the four types of spin transition materials: (1) Fe(II)-based spin crossover compounds, (2) Dithiooxalato-bridged Fe-based charge transfer systems, (3) Charge transfer active Prussian Blue Analogues, and (4) Copper(II)-octacyanidomolybdate(IV) photomagnetic materials. The download of this thematic issue is free of charge. Norimichi Kojima, Shin-ichi Ohkoshi and Seiji Miyashita (Eds.), Thematic Issue: Phase Transition and Dynamical Properties of Spin Transition Materials, Current Inorganic Chemistry, vol. 6, issue 1 (2016)

Millisecond Coherence Time in a Tunable Molecular Electronic Spin Qubit Millisecond coherence time for a coordination complex qubit was observed, surpassing the previous record for such a system by an order of magnitude. The results illuminate a path forward in synthetic design principles, which should unite CS2 solubility with nuclear spin free ligand fields to develop a new generation of molecular qubits. Joseph M. Zadrozny, Jens Niklas, Oleg G. Poluektov, and Danna E. Freedman, Millisecond Coherence Time in a Tunable Molecular Electronic Spin Qubit, ACS Cent. Sci. 1, 488-492 (2015)

Ring, Ring Long before molecular magnetism started, the advent of magnetic molecular rings was announce in a prophetic publication (Björn Benny & Agnetha Frida, Ring, Ring, Polar Music, 1973). In the early days only even-membered rings could be synthesized, odd rings were covered by strange theoretical prophecies (JMMM 220 (2000) 227; Phys. Rev. B 68 (2003) 054422). Ring, ring, why don't you give me a call? Ring, ring, the happiest sound of them all Ring, ring, I stare at the phone on the wall And I sit all alone impatiently Won't you please understand the need in me So, ring, ring, why don't you make an odd ring? 2016: here we go - an odd homometallic chromium ring is reported, which is the first regular Cr9 antiferromagnetic ring. Its electronic relaxation dynamics was probed by 1H-NMR, which allows to determine the spin-phonon coupling strength. At very low temperatures, the relaxation is characterized by a single dominating Arrhenius-type relaxation process, whereas several relevant processes emerge at higher temperatures. E. Garlatti, S. Bordignon, S. Carretta, G. Allodi, G. Amoretti, R. De Renzi, A. Lascialfari, Y. Furukawa, G. A. Timco, R. Woolfson, R. E. P. Winpenny, and P. Santini, Relaxation dynamics in the frustrated Cr9 antiferromagnetic ring probed by NMR, Phys. Rev. B 93, 024424 (2016) More stories on rings (Tell me, are we really through?): McInnes, E. J. L., Timco, G. A., Whitehead, G. F. S. and Winpenny, R. E. P. Heterometallic Rings: Their Physics and use as Supramolecular Building Blocks, Angew. Chem. Int. Ed., 54, 14244-14269 (2015) Alternative interpretation (R.W.: The ring was made by Alberich?!): Original publication:

Toward Tailored All-Spin Molecular Devices Molecular based spintronic devices offer great potential for future energy-efficient information technology as they combine ultimately small size, high-speed operation, and low-power consumption. Recent developments in combining atom-by-atom assembly with spin-sensitive imaging and characterization at the atomic level have led to a first prototype of an all-spin atomic-scale logic device, but the very low working temperature limits its application. Here, we show that a more stable spintronic device could be achieved using tailored Co-Salophene based molecular building blocks, combined with in situ electrospray deposition under ultrahigh vacuum conditions as well as control of the surface-confined molecular assembly at the nanometer scale. In particular, we describe the tools to build a molecular, strongly bonded device structure from paramagnetic molecular building blocks including spin-wires, gates, and tails. Such molecular device concepts offer the advantage of inherent parallel fabrication based on molecular self-assembly as well as an order of magnitude higher operation temperatures due to enhanced energy scales of covalent through-bond linkage of basic molecular units compared to substrate- mediated coupling schemes employing indirect exchange coupling between individual adsorbed magnetic atoms on surfaces. Maciej Bazarnik, Bernhard Bugenhagen, Micha Elsebach, Emil Sierda, Annika Frank, Marc H. Prosenc, Roland Wiesendanger, Toward Tailored All-Spin Molecular Devices, Nano Lett. 2016, 16, 577-582

The classical and quantum dynamics of molecular spins on graphene The investigation of graphene has become a central field in contemporary science, because of its superior properties and the profusion of physical phenomena that it has revealed. Several central issues remains unexplored, though: how does graphene interact with spins? can one modulate the spin behaviour via interactions with electrons? Answering these questions is important for information storage and logic devices, because graphene is hailed as a potentially ideal material in spintronics, but is largely diamangetic. The new research paper shows the effect of graphene phonons and electrons on the spin dynamics of molecules. The authors show that Dirac electrons introduce dominant quantum-relaxation channels and, allow reaching a quantum tunneling regime, called Villain's tunneling, that was predicted 20 years ago and never observed. A novel theoretical background is provided, fully explaining the data and setting the basis for the understanding of graphene-spin interactions. These observations have profound consequences for the design of graphene spin-processing devices and pave the way to coherent control of graphene-based spintronic devices that can be manipulated electrically. Christian Cervetti, Angelo Rettori, Maria Gloria Pini, Andrea Cornia, Ana Repolles, Fernando Luis, Martin Dressel, Stephan Rauschenbach, Klaus Kern, Marko Burghard, Lapo Bogani, The classical and quantum dynamics of molecular spins on graphene, Nature Materials 15 (2015) 164

Universal sequence of ground states validating the classification of frustration in antiferromagnetic rings with a single bond defect The sequence of 2s+1 ground states in the frustrated antiferromagnetic rings with odd number n of local spins s resulting from a single bond defect strength is determined, and occurrence of the Lieb-Mattis energy level ordering, proven for the bipartite systems only, is confirmed for the rings in question. The sequence is universal, provides the theoretical basis for the recent classification of spin frustration in molecular magnets, and indicates that the Lieb-Mattis theorem (LMT) consequences exist for the nonbipartite rings. The states in the sequence are characterized by the total spin S fulfilling the constraint S smaller than s and are separated by 2s Kahn degenerate frustration points. The possible LMT consequences in other systems are discussed. Grzegorz Kamieniarz, Wojciech Florek, and Micha Antkowiak, Universal sequence of ground states validating the classification of frustration in antiferromagnetic rings with a single bond defect, Phys. Rev. B 92, 140411 (2015)

Recent advances in the design of magnetic molecules for use as cryogenic magnetic coolants This review outlines recent advances in the design of 3d-, 4f-, and 3d-4f type magnetic molecules for use as excellent cryogenic magnetic coolants based on the magnetocaloric effect (MCE), and the structure- magnetocaloric correlations of reported molecular coolants. Further improvements in the MCE values of molecular magnetic materials are also proposed based on assembly strategies from molecular chemistry and crystal engineering. Jun-Liang Liu, Yan-Cong Chen, Fu-Sheng Guo, Ming-Liang Tong, Recent advances in the design of magnetic molecules for use as cryogenic magnetic coolants, Coordination Chemistry Reviews 281 (2014) 26-49

Pushing the limits of magnetic anisotropy in trigonal bipyramidal Ni(II) Monometallic complexes based on 3d transition metal ions in certain axial coordination environments can exhibit appreciably enhanced magnetic anisotropy, important for memory applications, due to stabilisation of an unquenched orbital moment. For high-spin trigonal bipyramidal Ni(II), if competing structural distortions can be minimised, this may result in an axial anisotropy that is at least an order of magnitude stronger than found for orbitally non-degenerate octahedral complexes. Broadband, high-field EPR studies of [Ni(MDABCO)2Cl3]ClO4 confirm an unprecedented axial magnetic anisotropy, which pushes the limits of the familiar spin-only description. Crucially, compared to complexes with multidentate ligands that encapsulate the metal ion, we see only a very small degree of axial symmetry breaking. The compound displays field-induced slow magnetic relaxation, which is rare for monometallic Ni(II) complexes due to efficient spin–lattice and quantum tunnelling relaxation pathways. Katie E. R. Marriott, Lakshmi Bhaskaran, Claire Wilson, Marisa Medarde, Stefan T. Ochsenbein, Stephen Hill, Mark Murrie, Pushing the limits of magnetic anisotropy in trigonal bipyramidal Ni(II), Chem. Sci., 6 (2015) 6823

A Single-Chain Magnet with a Very High Blocking Temperature and a Strong Coercive Field Two isostructural 1-D complexes were synthesized. These stable chains exhibit very strong intramolecular antiferromagnetic metal-radical exchange coupling. One compound shows slow magnetic relaxation behavior with a high blocking temperature of about 13.2 K and a very high coercive field of 49 kOe at 4.0 K. Rafael A. Allao Cassaro, Samira G. Reis, Thamyres S. Araujo, Paul M. Lahti, Miguel A. Novak, Maria G. F. Vaz, A Single-Chain Magnet with a Very High Blocking Temperature and a Strong Coercive Field, Inorg. Chem., 2015, 54 (19), 9381-9383

Thermodynamic observables of Mn12-acetate calculated for the full spin Hamiltonian Thirty-five years after its synthesis, magnetic observables are calculated for the molecular nanomagnet Mn12-acetate using a spin Hamiltonian that contains all spins. Starting from a very advanced density functional theory parametrization [V. V. Mazurenko et al., Phys. Rev. B 89, 214422 (2014)], we evaluate magnetization and specific heat for this anisotropic system of 12 manganese ions with a staggering Hilbert space dimension of 100 000 000 using the finite-temperature Lanczos method. We compare the results with those obtained from other parametrizations. Our investigations demonstrate that it is now possible to assess the quality of parametrizations of effective spin Hamiltonians for rather large magnetic molecules. Oliver Hanebaum and Jürgen Schnack, Thermodynamic observables of Mn12-acetate calculated for the full spin Hamiltonian, Phys. Rev. B 92, 064424 (2015)

Calorimetry of functional inorganic materials Bentham Science published three volumes of the thematic issue of 'Current Inorganic Chemistry' on 'calorimetry of functional inorganic materials' edited by Prof. Michio Sorai and Prof. Yasuiro Nakazawa. The thematic issue includes several contributions on molecular magnets. You can download for free the three editorials to make you an opinion of the high level of the issue. The three issues are available at: http://benthamscience.com/journal/contents.php?journalID=cic&issueID=126151 http://benthamscience.com/journal/contents.php?journalID=cic&issueID=124573 http://benthamscience.com/journal/contents.php?journalID=cic&issueID=124511 The first volume is available on a free access basis.

Magnetic materials Wiley-VCH opened a web page to present 'Magnetic Materials' as a Hot Topic. 'Magnetic phenomena are omnipresent in the modern world. The Nobel prize in Physics (2007) was awarded for studies of giant magnetoresistance to A. Fert and P. Grünberg; their discoveries were soon implemented in hard drives (see picture, courtesy of IBM Germany). Learn more about the current research into magnetic materials, basic or applied.' Link to the page: http://www.wiley-vch.de/util/hottopics/magnetic/

Tutorial Review: 3d single-ion magnets One of the determining factors in whether single-molecule magnets (SMMs) may be used as the smallest component of data storage, is the size of the barrier to reversal of the magnetisation, Ueff. This physical quantity depends on the magnitude of the magnetic anisotropy of a complex and the size of its spin ground state. In recent years, there has been a growing focus on maximising the anisotropy generated for a single 3d transition metal (TM) ion, by an appropriate ligand field, as a means of achieving higher barriers. Because the magnetic properties of these compounds arise from a single ion in a ligand field, they are often referred to as single-ion magnets (SIMs). Here, the synthetic chemist has a significant role to play, both in the design of ligands to enforce propitious splitting of the 3d orbitals and in the judicious choice of TM ion. Since the publication of the first 3d-based SIM, which was based on Fe(II), many other contributions have been made to this field, using different first row TM ions, and exploring varied coordination environments for the paramagnetic ions. Gavin A. Craig and Mark Murrie, Tutorial Review: 3d single-ion magnets, Chem. Soc. Rev. 44 (2015) 2135

Design Criteria for High-Temperature Single-Molecule Magnets Design criteria to obtain slow magnetic relaxation are theoretically investigated for two-coordinate complexes of Dy(III). It is shown that large energy barriers to magnetic relaxation, Ueff, can be achieved in the absence of near-linearity and generally that any two-coordinate complex of Dy(III) is an attractive synthetic target that may possess Ueff > 1000 cm–1. These large Ueff values are immediately diminished if axial ligation is disrupted by solvent coordination. Nicholas F. Chilton, Design Criteria for High-Temperature Single-Molecule Magnets, Inorg. Chem. 54 (2015) 2097

Self-trapping of charge polarized states in four-dot molecular quantum cellular automata: bi-electronic tetrameric mixed-valence species Our interest in this article is prompted by the problem of the vibronic self-trapping of charge polarized states in the four-dot molecular quantum cellular automata (mQCA), a paradigm for nanoelectronics, in which binary information is encoded in charge configuration of the mQCA cell. We report the evaluation of the electronic states and the adiabatic potentials of mixed-valence (MV) systems in which two electrons (or holes) are shared among four sites. These systems are exemplified by the two kinds of tetra-ruthenium (2Ru(II)+ 2Ru(III)) clusters (assembled as two coupled Creutz-Taube dimers) for which molecular implementation of mQCA was proposed. The tetra-ruthenium clusters include two holes shared among four sites and correspondingly we employ the model which takes into account the electron transfer processes as well as the Coulomb repulsion in the different instant positions of localization. The vibronic self-trapping is considered within the conventional vibronic Piepho, Krausz and Schatz (PKS) model adapted to the bi-electronic MV species with the square topology. This leads to a complicated vibronic problem for spin-singlet and spin-triplet states correspondingly. The adiabatic potentials are evaluated with account for the low lying Coulomb levels in which the antipodal sites are occupied, the case just actual for utilization in mQCA. The conditions for the vibronic localization in spin-singlet and spin-triplet states are revealed in terms of the two actual transfer pathways parameters and strength of the vibronic coupling. Boris Tsukerblat, Andrew Palii, Juan Modesto Clemente-Juan, Self-trapping of charge polarized states in four-dot molecular quantum cellular automata: bi-electronic tetrameric mixed-valence species, Pure and Applied Chemistry 87 (2014) 271

Supramolecular Recognition Influences Magnetism in [X@HVIV8VV14O54]6− Self-Assemblies with Symmetry-Breaking Guest Anions Mixed-valence polyoxovanadates(IV/V) have emerged as one of the most intricate class of supramolecular all-inorganic host species, able to encapsulate a wide variety of smaller guest templates during their self-assembly formation process. As showcased herein, the incorporation of guests, though governed solely by ultra-weak electrostatic and van der Waals interactions, can cause drastic effects on the electronic and magnetic characteristics of the shell complex of the polyoxovanadate. The authors address the question of methodology for the magnetochemical analysis of virtually isostructural polyoxoanions of D2d symmetry enclosing diamagnetic template anions. These induce different polarization effects related to differences in their geometric structures, symmetry, ion radii, and valence shells, eventually resulting in a supramolecular modulation of magnetic exchange between the V(3d) electrons that are partly delocalized. Kirill Yu. Monakhov, Oliver Linnenberg, Piotr Kozłowski, Jan van Leusen, Claire Besson, Tim Secker, Arkady Ellern, Xavier Lopez, Josep M. Poblet, Paul Kögerler, Supramolecular Recognition Influences Magnetism in [X@HVIV8VV14O54]6− Self-Assemblies with Symmetry-Breaking Guest Anions, Chem. Eur. J. 21, 2387 (2014)

Quantum signatures of a molecular nanomagnet in direct magnetocaloric measurements Geometric spin frustration in low-dimensional materials, such as the two-dimensional kagome or triangular antiferromagnetic nets, can significantly enhance the change of the magnetic entropy and adiabatic temperature following a change in the applied magnetic field, that is, the magnetocaloric effect. In principle, an equivalent outcome should also be observable in certain high-symmetry zero-dimensional, that is, molecular, structures with frustrated topologies. Here we report experimental realization of this in a heptametallic gadolinium molecule. Adiabatic demagnetization experiments reach approximately 200 mK, the first sub-Kelvin cooling with any molecular nanomagnet, and reveal isentropes (the constant entropy paths followed in the temperature-field plane) with a rich structure. The latter is shown to be a direct manifestation of the trigonal antiferromagnetic net structure, allowing study of frustration-enhanced magnetocaloric effects in a finite system. Joseph W. Sharples, David Collison, Eric J. L. McInnes, Jürgen Schnack, Elias Palacios, Marco Evangelisti, Quantum signatures of a molecular nanomagnet in direct magnetocaloric measurements, Nature Communications 5 (2014) 5321

Room temperature quantum coherence in a potential molecular qubit The successful development of a quantum computer would change the world, and current internet encryption methods would cease to function. However, no working quantum computer that even begins to rival conventional computers has been developed yet, which is due to the lack of suitable quantum bits. A key characteristic of a quantum bit is the coherence time. Transition metal complexes are very promising quantum bits, owing to their facile surface deposition and their chemical tunability. However, reported quantum coherence times have been unimpressive. Here we report very long quantum coherence times for a transition metal complex of 68 microseconds at low temperature (qubit figure of merit QM=3,400) and 1 microseconds at room temperature, much higher than previously reported values for such systems. We show that this achievement is because of the rigidity of the lattice as well as removal of nuclear spins from the vicinity of the magnetic ion. Katharina Bader, Dominik Dengler, Samuel Lenz, Burkhard Endeward, Shang-Da Jiang, Petr Neugebauer, Joris van Slageren, Room temperature quantum coherence in a potential molecular qubit, Nature Communications 5 (2014) 5304

Two is complicated enough! Lanthanide compounds show much higher energy barriers to magnetic relaxation than 3d-block compounds, and this has led to speculation that they could be used in molecular spintronic devices. Prototype molecular spin valves and molecular transistors have been reported, with remarkable experiments showing the influence of nuclear hyperfine coupling on transport properties. Modelling magnetic data measured on lanthanides is always complicated due to the strong spin-orbit coupling and subtle crystal field effects observed for the 4f-ions; this problem becomes still more challenging when interactions between lanthanide ions are also important. Such interactions have been shown to hinder and enhance magnetic relaxation in different examples, hence understanding their nature is vital. Here the authors are able to measure directly the interaction between two dysprosium(III) ions through multi-frequency electron paramagnetic resonance spectroscopy and other techniques, and explain how this influences the dynamic magnetic behaviour of the system. A series of water-bridged dinickel complexes has been synthesized and structurally characterized by X-ray crystallography. The magnetic properties have been probed by magnetometry and EPR spectroscopy, and detailed measurements show that the axial zero-field splitting, D, of the nickel(II) ions is on the same order as the isotropic exchange interaction, J, between the nickel sites. The isotropic exchange interaction can be related to the angle between the nickel centers and the bridging water molecule, while the magnitude of D can be related to the coordination sphere at the nickel sites. Eufemio Moreno Pineda, Nicholas F. Chilton, Raphael Marx, Maria Dörfel, Daniel O. Sells, Petr Neugebauer, Shang-Da Jiang, David Collison, Joris van Slageren, Eric J.L. McInnes & Richard E.P. Winpenny, Direct measurement of dysprosium(III)...dysprosium(III) interactions in a single-molecule magnet, Nature Communications 5 (2014) 5243 James P. S. Walsh, Stephen Sproules, Nicholas F. Chilton, Anne-Laure Barra, Grigore A. Timco, David Collison, Eric J. L. McInnes, and Richard E. P. Winpenny, On the Possibility of Magneto-Structural Correlations: Detailed Studies of Dinickel Carboxylate Complexes, Inorg. Chem. 53 (2014) 8464

First-principles modeling of magnetic excitations in Mn12 A fully microscopic theory of magnetic properties of the prototype molecular magnet Mn12 is developed. First, the intramolecular magnetic properties have been studied by means of first-principles density functional based methods, with local correlation effects being taken into account within the local density approximation plus U (LDA+U) approach. Using the magnetic force theorem, we have calculated the interatomic isotropic and anisotropic exchange interactions and full tensors of single-ion anisotropy for each Mn ion. Dzyaloshinskii-Moriya (DM) interaction parameters turned out to be unusually large, reflecting a low symmetry of magnetic pairs in molecules, in comparison with bulk crystals. Based on these results a distortion of ferrimagnetic ordering due to DM interactions is predicted. Further, the authors use an exact diagonalization approach allowing one to work with as large a Hilbert space dimension as 108 without any particular symmetry (the case of the constructed magnetic model). Based on the computational results for the excitation spectrum, we propose a distinct interpretation of the experimental inelastic neutron scattering spectra. V. V. Mazurenko, Y. O. Kvashnin, Fengping Jin, H. A. De Raedt, A. I. Lichtenstein, and M. I. Katsnelson, First-principles modeling of magnetic excitations in Mn12, Phys. Rev. B 89 (2014) 214422

S=1/2 One-Dimensional Random-Exchange Ferromagnetic Zigzag Ladder, Which Exhibits Competing Interactions in a Critical Regime The synthesis, crystal structure, and magnetic properties (from a combined experimental and First-Principles Bottom-Up theoretical study) of the new compound catena-dichloro(2-Cl-3Mpy)copper(II), 1, [2-Cl-3Mpy=2-chloro-3-methylpyridine] are described and rationalized. Crystals of 1 present well isolated magnetic 1D chains (no 3D order was experimentally observed down to 1.8 K) and magnetic frustration stemming from competing ferromagnetic nearest-neighbor (JNN) interactions and antiferromagnetic next-nearest neighbor (JNNN) interactions, in which JNNN/JNN <-0.25. These magnetic interactions give rise to a unique magnetic topology: a two-leg zigzag ladder composed of edge-sharing up-down triangles with antiferromagnetic interactions along the rails and ferromagnetic interactions along the zigzag chain that connects the rails. Crystals of 1 also present a random distribution of the 2-Cl-3Mpy groups, which are arranged in two different orientations, each with a 50 % occupancy. This translates into a random static structural disorder within each chain by virtue of which the value of the JNN magnetic interactions can randomly take one of three values. The structural disorder does not affect the JNNN value. A proper statistical treatment of this disorder provides a computed magnetic susceptibility curve that reproduces the main features of the experimental data. Susan N. Herringer, Merce Deumal, Jordi Ribas-Arino, Juan J. Novoa, Christopher P. Landee, Jan L. Wikaira, Mark M. Turnbull, S=1/2 One-Dimensional Random-Exchange Ferromagnetic Zigzag Ladder, Which Exhibits Competing Interactions in a Critical Regime, Chem. Eur. J. 20 (2014) 8355

Review: A gentle introduction to magnetism: units, fields, theory, and experiment In case you need a book on magnetism for your students, take this review: We present an introduction to the workings, units of measure, and general properties of magnetic materials. This is intended as a üprimer to interpretation of magnetic dataý for those who are entering the field, or those who are encountering magnetic measurements in the literature. We expect this work will serve as an initial guide to the reader to familiarize them with the basics in the hope that those working in the field of magnetochemistry will wish to explore additional, more detailed literature as their specific investigations demand. Topics covered include: magnetic fields and units (SI and cgs), paramagnetism (magnetization and magnetic susceptibility), Curie and Curie-Weiss behavior, magnetic exchange interactions, magnetic anisotropy, dimeric systems and exchange-coupled networks (including chains, ladders, and layers), and long-range order. Christopher P. Landee and Mark M. Turnbull, Review: A gentle introduction to magnetism: units, fields, theory, and experiment, Journal of Coordination Chemistry, 67 (2014) 375-439

Single-molecule magnet engineering: building-block approaches Tailoring the specific magnetic properties of any material relies on the topological control of the constituent metal ion building blocks. Although this general approach does not seem to be easily applied to traditional inorganic bulk magnets, coordination chemistry offers a unique tool to delicately tune, for instance, the properties of molecules that behave as "magnets", the so-called single-molecule magnets (SMMs). Although many interesting SMMs have been prepared by a more or less serendipitous approach, the assembly of predesigned, isolatable molecular entities into higher nuclearity complexes constitutes an elegant and fascinating strategy. This Feature article focuses on the use of building blocks or modules (both terms being used indiscriminately) to direct the structure, and therefore also the magnetic properties, of metal ion complexes exhibiting SMM behaviour. Kasper S. Pedersen, Jesper Bendix, Rodolphe Clerac, Single-molecule magnet engineering: building-block approaches, Chem. Comm. 33, 1084(2014)

Organometallic Single-Molecule Magnets Single-molecule magnets (SMMs) display slow relaxation of the magnetization, purely of molecular origin, in the absence of an applied magnetic field. This review summarizes the important role played by organometallic chemistry in the recent development of SMMs. The broad applicability of organometallic synthesis has led to a series of organometallic SMMs containing transition metals, lanthanides, or actinides, with several examples accounting for some of the most fascinating low-temperature magnetism. The review has two main aims. The first aim is to provide organometallic chemists with an introduction to one of the most exciting areas of modern molecular magnetism and, in particular, to highlight how organometallic chemistry has allowed the field to evolve in new directions. The second aim is more of a clarion call: organometallic chemistry still has hugely underexploited potential in the development of single-molecule magnets, and it is reasonable to expect that different synthetic approaches will lead to new and unusual magnetic phenomena. By using this review as an entry point for studying the literature in more detail, hopefully more organometallic chemists will consider directing their synthetic repertoire toward the design and realization of new, and possibly improved, single-molecule magnets. Richard A. Layfield, Organometallic Single-Molecule Magnets, Organometallics 33, 1084(2014)

A Cobalt Pyrenylnitronylnitroxide Single-Chain Magnet with High Coercivity and Record Blocking Temperature Coordination of a [Co(hfac)2] moiety (hfac=hexafluoroacetylacetonate) with a nitronylnitroxide radical linked to bulky, rigid pyrene (PyrNN) gives a helical 1:1 chain complex, in which both oxygen atoms of the radical NO. groups are bonded to CoII ions with strong antiferromagnetic exchange. The complex shows single-chain magnet (SCM) behavior with frequency-dependent magnetic susceptibility, field-cooled and zero-field-cooled susceptibility divergence with a high blocking temperature of around 14 K (a record among SCMs), and hysteresis with a very large coercivity of 32 kOe at 8 K. The magnetic behavior is partly related to good chain isolation induced by the large pyrene units. Two magnetic relaxation processes have been observed, a slower one attributable to longer, and a faster one attributable to short chains. No evidence of magnetic ordering has been found. Maria G. F. Vaz, Rafael A. Allao Cassaro, Handan Akpinar, John A. Schlueter, Paul M. Lahti, Miguel A. Novak, A Cobalt Pyrenylnitronylnitroxide Single-Chain Magnet with High Coercivity and Record Blocking Temperature, Chemistry - A European Journal 20, 5460 (2014)

Magnetochemical Complexity of Hexa- and Heptanuclear Wheel Complexes of Late-3d Ions Supported by N,O-Donor Pyridyl-Methanolate Ligands The scaffold geometries, stability and magnetic features of the (pyridine-2-yl)methanolate (L) supported wheel-shaped transition-metal complexes with compositions [M6L12] (1), [Na⊂(ML2)6]+ (2), and [M′⊂(ML2)6]2+ (3), in which M=CoII, NiII, CuII, and ZnII were investigated with density functional theory (DFT). The goals of this study are manifold: 1) To advance understanding of the magnetism in the synthesized compounds; 2) To disclose how the structural, electronic, and magnetic characteristics of the molecules change upon varying MII from d7 (Co2+) to d10 (Zn2+); 3) To estimate the influence of the Na+ and M′2+ ions (XQ+) occupying the central voids on the external and internal magnetic coupling interactions in these spin structures; 4) To assess the relative structural and electrochemical stabilities. In particular, the authors focus here on the net spin polarization, the determination of the strength and the sign of the exchange coupling energies, the rationalization of the nature of the magnetic coupling, and the ground-state structures. The study combines the broken symmetry DFT approach and the model Hamiltonian methodology implemented in the computational framework CONDON 2.0 for the modeling of molecular spin structures and to interpret magnetic susceptibility measurements. The authors illustrate that whereas the structures, stability and magnetism of 1, 2, and 3 are indeed influenced by the nature of 3d transition-metals in the {M6} rims, the XQ+ ions in the inner cavities of 2 and 3 impact these properties to an even larger degree. Kirill Yu. Monakhov, Xavier Lopez, Manfred Speldrich, Jan van Leusen, Paul Kögerler, Pierre Braunstein, Josep M. Poblet, Magnetochemical Complexity of Hexa- and Heptanuclear Wheel Complexes of Late-3d Ions Supported by N,O-Donor Pyridyl-Methanolate Ligands, Chemistry - A European Journal 20 (2014) 3769-3781

New Synthetic Route toward Heterometallic 3d-3d' and 3d-4f Single-Molecule Magnets. The First CoII-MnIII Heterometallic Complex Four tetranuclear heterometallic complexes, [CoII2Mn2III(dpm)4(MeO)6] (1) and [LnIII2MnIII2(dpm)6(MeO)6(MeOH)n], where Ln = Gd (2, n = 2), Tb (3, n = 2), and Dy (4, n = 0), have been obtained following the same general synthetic route, namely, the one-pot reaction between 2,2,6,6-tetrametil-3,5-heptanodione (Hdpm), MnCl2 and CoCl2 or Ln(NO3)3 in the presence of sodium methoxide. Within the four compounds, the metal ions bridged by methoxide ligands display a defect-diheterocubane core. Compounds 1, 3, and 4 show slow relaxation of the magnetization below 4 K. Guilherme P. Guedes, Stephane Soriano, Luiza A. Mercante, Nivaldo L. Speziali, Miguel A. Novak, Marius Andruh, and Maria G. F. Vaz, New Synthetic Route toward Heterometallic 3d-3d' and 3d-4f Single-Molecule Magnets. The First CoII-MnIII Heterometallic Complex, Inorg. Chem., 2013, 52, 8309-8311

Trend: Employing anisotropic exchange In a series of recent magnetic molecules 3d-5d exchange interactions are being employed. These interactions, as for instance in Mn(III)-Os(III)-Mn(III), are highly anisotropic. The hope is that properties of single-molecule magnets (SMM), such as the blocking temperature, can be improved using such compounds. Kasper S. Pedersen, Magnus Schau-Magnussen, Jesper Bendix, Hogni Weihe, Andrei V. Palii, Sophia I. Klokishner, Serghei Ostrovsky, Oleg S. Reu, Hannu Mutka, Philip L. W. Tregenna-Piggott, Enhancing the Blocking Temperature in Single-Molecule Magnets by Incorporating 3d-5d Exchange Interactions, Chemistry - A European Journal, 16, 13458-13464, 2010 Eva M. V. Kessler, Sebastian Schmitt and Christoph van Wüllen, Broken symmetry approach to density functional calculation of zero field splittings including anisotropic exchange interactions, J. Chem. Phys. 139, 184110 (2013) Jan Dreiser, Kasper S. Pedersen, Alexander Schnegg, Karsten Holldack, Joscha Nehrkorn, Marc Sigrist, Philip Tregenna-Piggott, Hannu Mutka, Hogni Weihe, Vladimir S. Mironov, Jesper Bendix, Oliver Waldmann, Three-Axis Anisotropic Exchange Coupling in the Single-Molecule Magnets NEt4[MnIII2(5-Brsalen)2(MeOH)2MIII(CN)6] (M=Ru, Os), Chemistry - A European Journal, 19, 3693-3701, 2013 Saurabh Kumar Singh, Gopalan Rajaraman, Can Anisotropic Exchange Be Reliably Calculated Using Density Functional Methods? A Case Study on Trinuclear Mn(III)-M(III)-Mn(III) (M=Fe, Ru, and Os) Cyanometalate Single-Molecule Magnets, Chemistry - A European Journal, 20, 113-123, 2014 Veronika Hoeke, Anja Stammler, Hartmut Bögge, Jürgen Schnack, and Thorsten Glaser, Strong and Anisotropic Superexchange in the Single-Molecule Magnet (SMM) [MnIII6OsIII]3+: Promoting SMM Behavior through 3d-5d Transition Metal Substitution, Inorg. Chem. 53 (2014) 257

A symbol approach for classification of molecule-based magnetic materials exemplified by coordination polymers of metal carboxylates The ever-growing family of molecule-based magnetic materials calls for a systematic classification of these structurally sophisticated and magnetically diverse compounds. Using magnetically active coordination polymers of metal carboxylates as representatives, the authors propose and illustrate in this review a symbol approach for their organization and categorization. By adopting this approach, the seemingly complex magneto-structural correlations in a wide variety of molecular magnetic materials, including single-molecule magnets, single-chain magnets, geometrically frustrated magnets, and high Curie-temperature magnets, can be readily discerned. Yan-Zhen Zheng, Zhiping Zheng,Xiao-Ming Chen, A symbol approach for classification of molecule-based magnetic materials exemplified by coordination polymers of metal carboxylates, Coordination Chemistry Reviews, 258-259 (2014) 1-15

An electrostatic model for the determination of magnetic anisotropy in dysprosium complexes Understanding the anisotropic electronic structure of lanthanide complexes is important in areas as diverse as magnetic resonance imaging, luminescent cell labelling and quantum computing. We present an intuitive strategy based on a simple electrostatic method, capable of predicting the magnetic anisotropy of dysprosium(III) complexes, even in low symmetry. The strategy relies only on knowing the X-ray structure of the complex and the well-established observation that, in the absence of high symmetry, the ground state of dysprosium(III) is a doublet quantized along the anisotropy axis with an angular momentum quantum number mJ ±15/2. The magnetic anisotropy axis of 14 low-symmetry mono-metallic dysprosium(III) complexes computed via high-level ab initio calculations are very well reproduced by our electrostatic model. Furthermore, we show that the magnetic anisotropy is equally well predicted in a selection of low-symmetry polymetallic complexes. Nicholas F. Chilton, David Collison, Eric J. L. McInnes, Richard E. P. Winpenny, and Alessandro Soncini, An electrostatic model for the determination of magnetic anisotropy in dysprosium complexes, Nature Communications, 2013, 4, 2551

Electrons in Molecules This book provides the reader with essential keys to a unified understanding of the rapidly expanding field of molecular materials and devices: electronic structures and bonding, magnetic, electrical and photo-physical properties, and the mastering of electrons in molecular electronics. Chemists will discover how basic quantum concepts allow usto understand the relations between structures, electronic structures, and properties of molecular entities and assemblies, and to design elaborate new molecules and useful materials. Physicists and engineers will realize how the molecular world fits in with their need for systems flexible enough to check theories or provide original solutions to exciting new scientific and technological challenges. The non-specialist will find out how molecules behave in electronics at the most minute, sub- nanosize level. Jean-Pierre Launay, Michel Verdaguer, Electrons in Molecules, Oxford University Press, 978-0-19-929778-8, Flyer and order form

Clusters of clusters In order to design and construct devices that take advantage of the magnetic properties of molecular nanomagnets, we must learn how to control the self-assembly of individual components. It has been demonstrated that {Cr7Ni} is a potential qubit candidate for quantum information processing and simulation with a well-defined two level quantum system with long phase memory lifetimes. Recent advances of the functionalisation of the periphery of {Cr7Ni} molecular nanomagnets with pyridyl and carboxylic acids groups, coupled with the controlled self-assembly of these with other molecular clusters and metal salts, has led to engineering of larger clusters-of-clusters constructs that could ultimately lead to the synthesis of devices using {Cr7Ni}. George F. S. Whitehead, Fabrizio Moro, Grigore A. Timco, Wolfgang Wernsdorfer, Simon J. Teat, Richard E. P. Winpenny, A Ring of Rings and Other Multicomponent Assemblies of Cages, Angewandte Chemie International Edition, Volume 52, Issue 38, pages 9932-9935, September 16, 2013 George F. S. Whitehead, Jesus Ferrando-Soria, Lorna G. Christie, Nicholas F. Chilton, Grigore A. Timco, Fabrizio Moroa, Richard E. P. Winpenny, The acid test: the chemistry of carboxylic acid functionalised {Cr7Ni} rings, Chem. Sci., 2014, Advance Article Please click on the pictures to see animations.

Frustration, frustration, frustration The term frustration is heavily used to explain many properties of magnetic materials, but it also seems to cause frustration among scientists. Read the following contributions: Key Role of Frustration in Suppression of Magnetization Blocking in Single-Molecule Magnets State-of-the-art ab initio calculations of a series of endohedral fullerenes are performed, and their anisotropic magnetic properties are described from the first principles. Contrary to general expectation that molecules of higher nuclearity exhibit better magnetic blocking properties, we predict Dy3N@C80 to be a relatively weak single-molecule magnet due to its frustrated ground state. This finding, relevant to polynuclear magnetic molecules in general, demonstrates the crucial role played by magnetic frustration in the suppression of magnetization blocking in single-molecule magnets. Veacheslav Vieru , Liviu Ungur , and Liviu F. Chibotaru, Key Role of Frustration in Suppression of Magnetization Blocking in Single-Molecule Magnets, J. Phys. Chem. Lett. 4, 3565 (2013) A classification of spin frustration in molecular magnets from a physical study of large odd-numbered-metal, odd electron rings The term "frustration" in the context of magnetism was originally used by P. W. Anderson and quickly adopted for application to the description of spin glasses and later to very special lattice types, such as the kagomé. The original use of the term was to describe systems with competing antiferromagnetic interactions and is important in current condensed matter physics in areas such as the description of emergent magnetic monopoles in spin ice. Within molecular magnetism, at least two very different definitions of frustration are used. Here we report the synthesis and characterization of unusual nine-metal rings, using magnetic measurements and inelastic neutron scattering, supported by density functional theory calculations. These compounds show different electronic/magnetic structures caused by frustration, and the findings lead us to propose a classification for frustration within molecular magnets that encompasses and clarifies all previous definitions. Michael L. Baker, Grigore A. Timco, Stergios Piligkos, Jennifer S. Mathieson, Hannu Mutka, Floriana Tuna, Piotr Kozlowski, Michal Antkowiak, Tatiana Guidi, Tulika Gupta, Harapriya Rath, Robert J. Woolfson, Grzegorz Kamieniarz, Robin G. Pritchard, Hogni Weihe, Leroy Cronin, Gopalan Rajaraman, David Collison, Eric J. L. McInnes, and Richard E. P. Winpenny, A classification of spin frustration in molecular magnets from a physical study of large odd-numbered-metal, odd electron rings, PNAS November 20, 2012 vol. 109 no. 47 19113-19118 Effects of frustration on magnetic molecules: a survey from Olivier Kahn until today In magnetism, of which molecular magnetism is a part, the term frustration is used rather sloppily. Sometimes one gains the impression that if the reason for some phenomenon is not quite clear then it is attributed to frustration. In this paper a discussion of the effects of frustration that are relevant for the field of molecular magnetism is presented. As will become clear later these effects indeed lead to a variety of unusual magnetic properties. J. Schnack, Effects of frustration on magnetic molecules: a survey from Olivier Kahn until today, Dalton Trans., 2010,39, 4677-4686

Dynamic control of magnetic nanowires by light-induced domain-wall kickoffs Magnetic relaxation processes were first discussed for a crystal of paramagnetic transition ions. It was suggested that mechanical vibrations of the crystal lattice (phonons) modulate the crystal electric field of the magnetic ion, thus inducing a direct relaxation between two different spin states. Direct relaxation has also been predicted for single-molecule magnets with a large spin and a high magnetic anisotropy and was first demonstrated in a Mn12 acetate crystal. The spin-lattice relaxation time for such a direct transition is limited by the phonon density of states at the spin resonance. In a three-dimensional system, such as a single-molecule magnet crystal, the phonon energy spectrum is continuous, but in a one-dimensional system, like a suspended carbon nanotube, the spectrum is discrete and can be engineered to an extremely low density of states. An individual single-molecule magnet, coupled to a suspended carbon nanotube, should therefore exhibit extremely long relaxation times and the system's reduced size should result in a strong spin-phonon coupling. Here, we provide the first experimental evidence for a strong spin-phonon coupling between a single molecule spin and a carbon nanotube resonator, ultimately enabling coherent spin manipulation and quantum entanglement. W. Wernsdorfer, Dynamic control of magnetic nanowires by light-induced domain-wall kickoffs, Nature Nanomaterials 8, 165 (2013)

Emerging young scientists in molecular magnetism Rodolphe Clerac (editor) writes: "Over the past thirty years, a range of nanosized metal complexes have been engineered by molecular chemists to exhibit original physical and magnetic properties, which include single-molecule magnet (SMM), single-chain magnet (SCM), spincrossover (SCO), high TC magnets and photomagnetism. More recent activity has focused on strategies to combine many of these properties to systematically produce multifunctional materials. Among these are chirality, conductivity, guest molecule adsorption, soft-matter properties (liquid-crystals, gels) and nanoparticle assembly, etc... Indeed by controlling self-assembly reactions and chemically modifying the molecular precursors utilized, creative chemists can finely tune these properties at the atomic scale, and contribute to a better understanding of the factors necessary for the integration of these molecular systems into future spintronics or molecular electronics applications. In this research field devoted to molecule-based magnetic materials, a new generation of scientists has recently emerged and it is the purpose of this special issue of Current Inorganic Chemistry on Molecular Magnetism to highlight some of the most recent work of these young researchers. Of course, not everyone was able to contribute to this issue and we hope to produce a second special issue on this topic to give a timely accounting of this flourishing research field in the future." All papers are available on line for free: LINK

Surface-Confined Electroactive Molecules for Multistate Charge Storage Information Bi-stable molecular systems with potential for applications in binary memory devices are raising great interest for device miniaturization. Particular appealing are those systems that operate with electrical inputs since they are compatible with existing electronic technologies. The processing of higher memory densities in these devices could be accomplished by increasing the number of memory states in each cell, although this strategy has not been much explored yet. In the article the authos highlight the recent advances devoted to the fabrication of charge-storage molecular surface-confined devices exhibiting multiple states. Mainly, this goal has been realized immobilizing a variety (or a combination) of electroactive molecules on a surface, although alternative approaches employing non-electroactive systems have also been described. Undoubtedly, the use of molecules with chemically tunable properties and nanoscale dimensions are raising great hopes for the devices of the future in which molecules can bring new perspectives such as multistability. M. Mas-Torrent, C. Rovira, J. Veciana, Surface-Confined Electroactive Molecules for Multistate Charge Storage Information, Advanced Materials 25 (2013) 462

Dynamic control of magnetic nanowires by light-induced domain-wall kickoffs Controlling the speed at which systems evolve is a challenge shared by all disciplines, and otherwise unrelated areas use common theoretical frameworks towards this goal. A particularly widespread model is Glauber dynamics, which describes the time evolution of the Ising model and can be applied to any binary system. In the article it is shown, using molecular nanowires under irradiation, that Glauber dynamics can be controlled by a novel domain-wall kickoff mechanism. In contrast to known processes, the kickoff has unambiguous fingerprints, slowing down the spin-flip attempt rate by several orders of magnitude, and following a scaling law. The required irradiance is very low, a substantial improvement over present methods of magneto-optical switching. These results provide a new way to control and study stochastic dynamic processes. Being general for Glauber dynamics, they can be extended to different kinds of magnetic nanowires and to numerous fields, ranging from social evolution to neural networks and chemical reactivity. Eric Heintze, Fadi El Hallak, Conrad Clauß, Angelo Rettori, Maria Gloria Pini, Federico Totti, Martin Dressel, Lapo Bogani, Dynamic control of magnetic nanowires by light-induced domain-wall kickoffs, Nature Materials 12 (2013) 202

Magnetic cluster excitations Magnetic clusters, i.e., assemblies of a finite number (between two or three and several hundred) of interacting spin centers which are magnetically decoupled from their environment, can be found in many materials ranging from inorganic compounds and magnetic molecules to artificial metal structures formed on surfaces and metalloproteins. Their magnetic excitation spectra are determined by the nature of the spin centers and of the magnetic interactions, and the particular arrangement of the mutual interaction paths between the spin centers. Small clusters of up to four magnetic ions are ideal model systems in which to examine the fundamental magnetic interactions, which are usually dominated by Heisenberg exchange, but often complemented by anisotropic and/or higher-order interactions. In large magnetic clusters, which may potentially deal with a dozen or more spin centers, there is the possibility of novel many-body quantum states and quantum phenomena. In this review the necessary theoretical concepts and experimental techniques to study the magnetic cluster excitations and the resulting characteristic magnetic properties are introduced, followed by examples of small clusters, demonstrating the enormous amount of detailed physical information that can be retrieved. The current understanding of the excitations and their physical interpretation in the molecular nanomagnets which represent large magnetic clusters is then presented, with a section devoted to the subclass of single-molecule magnets, distinguished by displaying quantum tunneling of the magnetization. Finally, there is a summary of some quantum many-body states which evolve in magnetic insulators characterized by built-in or field-induced magnetic clusters. The review concludes by addressing future perspectives in the field of magnetic cluster excitations. Albert Furrer, Oliver Waldmann, Magnetic cluster excitations, Rev. Mod. Phys. 85 (2013) 367

Switchable materials: A new spin on bistability Many different kinds of switchable molecules and materials are based on transition metal ions, but similar properties are also possible in organic materials. Now, two separate studies reveal new insights into the ability of organic radicals to associate reversibly and cooperatively in the solid state, and in so doing create bistable, hysteretic materials. The solid-state electronic structure and properties of a phenalenyl-based butyl-substituted neutral radical, that shows a hysteretic phase transition just above room temperature have been investigated. The electron density distribution of this radical throughout both branches of the hysteretic phase transition was analyzid using solid-state X-ray structures and two distinct electronic states were found in the hysteresis loop that accompanies the phase transition. The bistability of the two electronic states was observed through a number of measurements, including IR transmittance spectra of single crystals in the vicinity of the phase transition. Sushanta K. Pal, Pradip Bag, Arindam Sarkar, Xiaoliu Chi, Mikhail E. Itkis, Fook S. Tham, Bruno Donnadieu, and Robert C. Haddon, Hysteretic Spin and Charge Delocalization in a Phenalenyl-Based Molecular Conductor, JACS 132 (2010) 17258 Robin G. Hicks, Switchable materials: A new spin on bistability, Nature Chemistry 3 (2011) 189

Inelastic Neutron Scattering at its height INS is as powerful as it has never been before. Read the three following highlights to understand its success and importance for nowadays research in quantum magnetism. Spin dynamics of molecular nanomagnets unravelled at atomic scale by four-dimensional inelastic neutron scattering Molecular nanomagnets are among the first examples of finite-size spin systems and have been test beds for addressing several phenomena in quantum dynamics. In fact, for short-enough timescales the spin wavefunctions evolve coherently according to an appropriate spin Hamiltonian, which can be engineered to meet specific requirements. Unfortunately, so far it has been impossible to determine these spin dynamics directly. Here we show that recently developed instrumentation yields the four-dimensional inelastic-neutron scattering function in vast portions of reciprocal space and enables the spin dynamics to be determined directly. We use the Cr8 antiferromagnetic ring as a benchmark to demonstrate the potential of this approach which allows us, for example, to examine how quantum fluctuations propagate along the ring or to test the degree of validity of the Neel-vector-tunnelling framework. Michael L. Baker, Tatiana Guidi, Stefano Carretta, Jacques Ollivier, Hannu Mutka, Hans U. Güdel, Grigore A. Timco, Eric J. L. McInnes, Giuseppe Amoretti, Richard E. P. Winpenny, Paolo Santini, Spin dynamics of molecular nanomagnets unravelled at atomic scale by four-dimensional inelastic neutron scattering, Nature Physics 8 (2012) 906 See also this nice work: Michael L. Baker, Grigore A. Timco, Stergios Piligkos, Jennifer S. Mathieson, Hannu Mutka, Floriana Tuna, Piotr Kozlowski, Michal Antkowiak, Tatiana Guidi, Tulika Gupta, Harapriya Rath, Robert J. Woolfson, Grzegorz Kamieniarz, Robin G. Pritchard, Hogni Weihe, Leroy Cronin, Gopalan Rajaraman, David Collison, Eric J. L. McInnes, and Richard E. P. Winpenny, A classification of spin frustration in molecular magnets from a physical study of large odd-numbered-metal, odd electron rings, , PNAS (2012) Discrete antiferromagnetic spin-wave excitations in the giant ferric wheel Fe18 The low-temperature elementary spin excitations in the AFM molecular wheel Fe18 were studied experimentally by inelastic neutron scattering and theoretically by modern numerical methods, such as dynamical density matrix renormalization group or quantum Monte Carlo techniques, and analytical spin-wave theory calculations. Fe18 involves eighteen spin-5/2 FeIII ions with a Hilbert space dimension of 1014, constituting a physical system that is situated in a region between microscopic and macroscopic. The combined experimental and theoretical approach allowed us to characterize and discuss the magnetic properties of Fe18 in great detail. It is demonstrated that physical concepts such as the rotational-band or L and E-band concepts developed for smaller rings are still applicable. In particular, the higher-lying low-temperature elementary spin excitations in Fe18 or AFM wheels, in general, are of discrete antiferromagnetic spin-wave character. J. Ummethum, J. Nehrkorn, S. Mukherjee, N. B. Ivanov, S. Stuiber, Th. Strässle, P. L. W. Tregenna-Piggott, H. Mutka, G. Christou, O. Waldmann, J. Schnack, Discrete antiferromagnetic spin-wave excitations in the giant ferric wheel Fe18, Phys. Rev. B 86 (2012) 104403 Ferromagnetic Cluster Spin Waves in Molecular Disks Studied by Inelastic Neutron Scattering Structurally, the two mixed-valence manganese disks Mn7-11 and Mn7-16 differ only in the peripheral ligand but, as a result of a subtle interplay of intramolecular exchange interactions, differ strongly in their magnetic properties, e.g., Mn7-11 possesses a ground-state spin of S=11 and Mn7-16 of S=16. The exchange interactions in the disks were studied by inelastic neutron scattering. The analysis of the Q dependence of the observed magnetic transition intensities reveals that ferromagnetic cluster spin-wave excitations were observed. In this framework, it was possible to successfully model the experimental data and provide a physical understanding of the magnetism in the two disks. J. Nehrkorn, S. Mukherjee, S. Stuiber, H. Mutka, Th. Strässle, G. Christou, O. Waldmann, Ferromagnetic Cluster Spin Waves in Molecular Disks Studied by Inelastic Neutron Scattering, Phys. Rev. B 86 (2012) 134417

Hysteresis in the ground and excited spin state up to 10 T of a [MnIII6MnIII]3+ triplesalen single-molecule magnet We have synthesized the triplesalen-based single-molecule magnet (SMM) [MnIII6MnIII]3+ as a variation of our SMM [MnIII6CrIII](BPh4)3. The use of the rod-shaped anion lactate (lac) was intended to enforce a rod packing and resulted in the crystallization of [MnIII6MnIII](lac)3 in the highly symmetric space group R-3-bar. This entails a crystallographic S6 symmetry of the [MnIII6MnIII]3+ molecules, which in addition are all aligned with the crystallographic c axis. Moreover, the molecular environment of each [MnIII6MnIII]3+ molecule is highly symmetric. Single-crystals of [MnIII6MnIII](lac)3 exhibit a double hysteresis at 0.3 K with a hysteretic opening not only for the spin ground state up to 1.8 T, but also for an excited state becoming the ground state at about 3.4 T with a hysteretic opening up to 10 T. Ab initio calculations including spin-orbit coupling establish a non-magnetic behavior of the central MnIII low-spin (l.s.) ion at low temperatures, demonstrating that predictions from ligand-field theory are corroborated in the case of MnIII l.s. by ab intio calculations. Simulations of the field- and temperature-dependent magnetization data indicate that [MnIII6MnIII]3+ is in the limit of weak exchange with antiferromagnetic interactions in the trinuclear MnIII3 triplesalen subunits resulting in intermediate S* = 2 spins. Slight ferromagnetic interactions between the two trinuclear MnIII3 subunits lead to a ground state in zero-field that is approximately described by a total spin quantum number S = 4. This ground state exhibits only a very small anisotropy barrier due to the misalignment of the local zero-field splitting tensors. At higher magnetic fields of about 3.4 T, the spin configuration changes to an all-up orientation of the local MnIII spins, with the main part of the Zeeman energy needed for the spin-flip being required to overcome the local MnIII anisotropy barriers, while only minor contributions of the Zeeman energy are needed to overcome the antiferromagnetic interactions. These combined theoretical analyses provide a clear picture of the double-hysteretic behavior of the [MnIII6MnIII]3+ single-molecule magnet with hysteretic openings up to 10 T. Veronika Hoeke, Klaus Gieb, Paul Müller, Liviu Ungur, Liviu F. Chibotaru, Maik Heidemeier, Erich Krickemeyer, Anja Stammler, Hartmut Bögge, Christian Schröder, Jürgen Schnack, Thorsten Glaser, Hysteresis in the ground and excited spin state up to 10 T of a [MnIII6MnIII]3+ triplesalen single-molecule magnet, Chem. Sci. 3 (2012) 2868

Electronic read-out of a single nuclear spin using a molecular spin transistor Quantum control of individual spins in condensed-matter devices is an emerging field with a wide range of applications, from nanospintronics to quantum computing. The electron, possessing spin and orbital degrees of freedom, is conventionally used as the carrier of quantum information in proposed devices. However, electrons couple strongly to the environment, and so have very short relaxation and coherence times. It is therefore extremely difficult to achieve quantum coherence and stable entanglement of electron spins. Alternative concepts propose nuclear spins as the building blocks for quantum computing, because such spins are extremely well isolated from the environment and less prone to decoherence. However, weak coupling comes at a price: it remains challenging to address and manipulate individual nuclear spins. In this publication it is shown that the nuclear spin of an individual metal atom embedded in a single-molecule magnet can be read out electronically. The observed long lifetimes (tens of seconds) and relaxation characteristics of nuclear spin at the single-atom scale open the way to a completely new world of devices in which quantum logic may be implemented. Romain Vincent, Svetlana Klyatskaya, Mario Ruben, Wolfgang Wernsdorfer, Franck Balestro, Electronic read-out of a single nuclear spin using a molecular spin transistor, Nature 488 (2012) 357

How good can spin densities be calculated? An approach for the calculation of spin density distributions for molecules is presented, that require very large active spaces for a qualitatively correct description of their electronic structure. It is based on the density-matrix renormalization group (DMRG) algorithm to calculate the spin density matrix elements as a basic quantity for the spatially resolved spin density distribution. The spin density matrix elements are directly determined from the second-quantized elementary operators optimized by the DMRG algorithm. As an analytic convergence criterion for the spin density distribution, we employ our recently developed sampling-reconstruction scheme to build an accurate complete-active-space configuration-interaction (CASCI) wave function from the optimized matrix product states. The spin density matrix elements can then also be determined as an expectation value employing the reconstructed wave function expansion. Furthermore, the explicit reconstruction of a CASCI-type wave function provides insight into chemically interesting features of the molecule under study such as the distribution of alpha and beta electrons in terms of Slater determinants, CI coefficients, and natural orbitals. The methodology is applied to an iron nitrosyl complex which we have identified as a challenging system for standard approaches. Katharina Boguslawski, Konrad H. Marti, Örs Legeza, and Markus Reiher, Accurate ab Initio Spin Densities, J. Chem. Theory Comput., 2012, 8 (6), pp 1970-1982

Fragmenting Gadolinium: Mononuclear Polyoxometalate-Based Magnetic Coolers for Ultra-Low Temperatures The polyoxometalate clusters with formula [Gd(W5O18)2] and [Gd(P5W30O110)] each carry a single magnetic ion of gadolinium, which is the most widespread element among magnetic refrigerant materials. In an adiabatic demagnetization, the lowest attainable temperature is limited by the presence of magnetic interactions that bring about magnetic order below a critical temperature. The authors demonstrate that this limitation can be overcome by chemically engineering the molecules in such a way to effectively screen all magnetic interactions, suggesting their use as ultra-low-temperature coolers. Martinez-Perez, Maria-Jose and Montero, Oscar and Evangelisti, Marco and Luis, Fernando and Sese, Javier and Cardona-Serra, Salvador and Coronado, Eugenio, Fragmenting Gadolinium: Mononuclear Polyoxometalate-Based Magnetic Coolers for Ultra-Low Temperatures, Adv. Mater. 24 (2012) 4301-4305

Inelastic neutron scattering studies on the odd-membered antiferromagnetic wheel Cr8Ni Roughly 50 % of Europe's molecular magnetism community contributed to the following article: A detailed characterization of the magnetic properties of the odd-membered antiferromagnetic "wheel" Cr8Ni has been conducted. Inelastic neutron scattering (INS) is used to investigate the energy and momentum transfer dependence of the low-lying spin excitations, including excited states inaccessible by other experimental techniques. The richness of the INS data, in conjunction with microscopic spin Hamiltonian simulations, enables an accurate characterization of the magnetic properties of Cr8Ni. Nearest-neighbor exchange constants of JCrCr = 1.31 meV and JCrNi = 3.22 meV are determined, and clear evidence of axial single-ion anisotropy is found. The parameters determined by INS are shown to fit magnetic susceptibility. The spectroscopic identification of several successive S=1 excited total spin states and lowest spin band excitations show that the rotational band picture, valid for bipartite AFM wheels, breaks down for this odd-numbered wheel. The exchange constants determined here differ from previous efforts based on bulk measurements, and possible reasons are discussed. The large JCrNi/JCrCr ratio in Cr8Ni puts this wheel into a regime with strong quantum fluctuations in which the ground state can be described with a valence bond solid state picture. Michael L. Baker, Oliver Waldmann, Stergios Piligkos, Roland Bircher, Olivier Cador, Stefano Carretta, David Collison, Felix Fernandez-Alonso, Eric J. L. McInnes, Hannu Mutka, Andrew Podlesnyak, Floriana Tuna, Stefan Ochsenbein, Roberta Sessoli, Andreas Sieber, Grigore A. Timco, Hogni Weihe, Hans U. Güdel, and Richard E. P. Winpenny, Inelastic neutron scattering studies on the odd-membered antiferromagnetic wheel Cr8Ni, Phys. Rev. B 86, 064405 (2012)

Self-Assembled Monolayer of Cr7Ni Molecular Nanomagnets by Sublimation We show, by complementary spectroscopic and STM analysis, that Cr7Ni derivatives are suitable to be sublimed in UHV conditions. Cr7Ni-bu weakly bonds to gold surface and can diffuse relatively freely on it, forming monolayers with hexagonal 2D packing. Conversely, by adding a functional thiol group to the central dibutylamine, a covalent bond between the molecule and surface gold adatoms is promoted, leading to a strong molecular grafting and the formation of a disordered monolayer. These two examples demonstrate the possibility to control the assembly of a large molecular complex, as rationalized by DFT calculations that establish different energy scales in the deposition processes. Moreover, low-temperature XMCD sprectra show that the magnetic features of Cr7Ni rings deposited in UHV on gold remain unchanged with respect to those of the corresponding bulk sample. Alberto Ghirri, Valdis Corradini, Valerio Bellini, Roberto Biagi, Umberto del Pennino, Valentina De Renzi, Julio C. Cezar, Christopher A. Muryn , Grigore A. Timco , Richard E. P. Winpenny , and Marco Affronte, Self-Assembled Monolayer of Cr7Ni Molecular Nanomagnets by Sublimation, ACS Nano, 2011, 5 (9), pp 7090-7099

Ultrafast Spin Avalanches in Crystals of Nanomagnets in Terms of Magnetic Detonation Recent experiments [W. Decelle et al., Phys. Rev. Lett. 102, 027203 (2009)] have discovered ultrafast propagation of spin avalanches in crystals of nanomagnets, which is 3 orders of magnitude faster than the traditionally studied magnetic deflagration. The new regime has been hypothetically identified as magnetic detonation. Here we demonstrate unequivocally the possibility of magnetic detonation in the crystals, as a front consisting of a leading shock and a zone of Zeeman energy release. We study the key features of the process and find that the magnetic detonation speed only slightly exceeds the sound speed in agreement with the experimental observations. For combustion science, our results provide a unique physical example of extremely weak detonation. M. Modestov, V. Bychkov, and M. Marklund, Ultrafast Spin Avalanches in Crystals of Nanomagnets in Terms of Magnetic Detonation, Phys. Rev. Lett. 107, 207208 (2011)

Theoretical Study of Exchange Coupling in 3d-Gd Complexes: Large Magnetocaloric Effect Systems Polynuclear 3d transition metal-Gd complexes are good candidates to present large magnetocaloric effect. This effect is favored by the presence of weak ferromagnetic exchange interactions that have been investigated using methods based on Density Functional Theory.The results show the crucial role of the Gd 5d orbitals in the exchange interaction while the 6s orbital seems to have a negligible participation. The analysis of the atomic and orbital spin populations reveals that the presence of spin density in the Gd 5d orbital is mainly due to a spin polarization effect, while a delocalization mechanism from the 3d orbitals of the transition metal can be ruled out. We propose a numerical DFT approach using pseudopotentials to calculate the exchange coupling constants in four polynuclear first-row transition metal-Gd complexes. Despite the complexity of the studied systems, the numerical approach gives coupling constants in excellent agreement with the available experimental data and, in conjunction with exact diagonalization methods (or Monte Carlo simulations), it makes it possible to obtain theoretical estimates of the entropy change due to the magnetization/demagnetization process of the molecule. Eduard Cremades , Silvia Gomez-Coca , Daniel Aravena , Santiago Alvarez , and Eliseo Ruiz, Theoretical Study of Exchange Coupling in 3d-Gd Complexes: Large Magnetocaloric Effect Systems, J. Am. Chem. Soc., 2012, 134 (25), pp 10532-10542

Molecular Cluster Magnets This work covers new developments in the field of molecular nanomagnetism, complementing previous books in this area. The book is written by experts in the field and is intended as a compilation of critical reviews of new areas rather than a comprehensive text. Contents: Supramolecular Polymetallic 2D [n x n] Transition Metal Grids – Approaches to Ordered Molecular Assemblies and Functional Molecular Devices (Laurence K Thompson, Louise N Dawe and Konstantin V Shuvaev) Recent Synthetic Results Involving Single Molecule Magnets (Guillem Aromí, Eric J L McInnes and Richard E P Winpenny) The Nanoscopic V15 Cluster: A Unique Magnetic Polyoxometalate (Boris Tsukerblat and Alex Tarantul) Neutron Spectroscopy of Molecular Nanomagnets (Tatiana Guidi) Recent Developments in EPR Spectroscopy of Molecular Nanomagnets (Eric J L McInnes) Simulating Computationally Complex Magnetic Molecules (Larry Engelhardt and Christian Schröder) World Scientific Series in Nanoscience and Nanotechnology- Vol. 3, MOLECULAR CLUSTER MAGNETS, edited by Richard Winpenny (The University of Manchester, UK), 312pp, 978-981-4322-94-2 & 978-981-4322-95-9(ebook)

Single-molecule magnets in carbon nanotubes Next-generation electronic, photonic or spintronic devices will be based on nanoscale functional units, such as quantum dots, isolated spin centres or single-molecule magnets. The key challenge is the coupling of the nanoscale units to the macroscopic world, which is essential for read and write purposes. Carbon nanotubes with one macroscopic and two nanoscopic dimensions provide an excellent means to achieve this coupling. Although the dimensions of nanotube internal cavities are suitable for hosting a wide range of different molecules, to our knowledge, no examples of molecular magnets inserted in nanotubes have been reported up to date. Here, we report on the successful encapsulation of single-molecule magnets in carbon nanotubes yielding a new type of hybrid nanostructure that combines all the key single-molecule magnet properties of the guest-molecules with the functional properties of the host-nanotube. This breakthrough paves the way for the construction of spintronic or ultrahigh-density magnetic data storage devices. Maria del Carmen Gimenez-Lopez, Fabrizio Moro, Alessandro La Torre, Carlos J. Gomez-Garcia, Paul D. Brown, Joris van Slageren, Andrei N. Khlobystov, Encapsulation of single-molecule magnets in carbon nanotubes, Nature Communications 2, 407 (2011)

A delocalized arene-bridged diuranium single-molecule magnet Single-molecule magnets (SMMs) are multinuclear clusters whose behaviour typically relies on intramolecular spin-coupling interactions between neighbouring metal ions. A diuranium-arene complex has now been prepared that shows behaviour characteristic of an SMM without relying on this type of superexchange mechanism. This may enable the construction of SMMs that maintain their magnetism at higher temperatures. David P. Mills, Fabrizio Moro, Jonathan McMaster, Joris van Slageren, William Lewis, Alexander J. Blake, Stephen T. Liddle, A delocalized arene-bridged diuranium single-molecule magnet, Nature Chemistry, 3, 454 - 460 (2011)

Magnetic Ground-State and Systematic X-ray Photoreduction Studies of an Iron-Based Star-Shaped Complex XPS methods are valuable tools in order to characterize magnetic substances, but radiation damages might spoil the investigation. In a recent paper a the star-shaped iron-based single-molecule magnet is investigated in order to clarify some open questions concerning the exact electronic and magnetic properties. To this end the internal magnetic structure is studied by applying X-ray magnetic circular dichroism to the Fe L2,3 edges and the occuring radiation photochemistry is investigated. A Fe3+ to Fe2+ photoreduction process, taking place under soft X-ray radiation, is reported. Karsten Kuepper, Christian Taubitz, Daniel Taubitz, Ulf Wiedwald, Andreas Scheurer, Stefan Sperner, Rolf W. Saalfrank, Jean-Paul Kappler, Loc Joly, Paul Ziemann, and Manfred Neumann, Magnetic Ground-State and Systematic X-ray Photoreduction Studies of an Iron-Based Star-Shaped Complex, J. Phys. Chem. Lett., 2011, 2 (13), pp 1491-1496

Supramolecular spin valves Magnetic molecules are potential building blocks for the design of spintronic devices. Moreover, molecular materials enable the combination of bottom-up processing techniques, for example with conventional top-down nanofabrication. In a new publication the authors present an original spin-valve device in which a non-magnetic molecular quantum dot, made of a single-walled carbon nanotube contacted with non-magnetic electrodes, is laterally coupled through supramolecular interactions to TbPc2 single-molecule magnets (Pc=phthalocyanine). Their localized magnetic moments lead to a magnetic field dependence of the electrical transport through the single-walled carbon nanotube, resulting in magnetoresistance ratios up to 300% at temperatures less than 1 K. M. Urdampilleta, S. Klyatskaya, J-P. Cleuziou, M. Ruben, W. Wernsdorfer, Supramolecular spin valves, Nature Materials 10, 502-506 (2011)

World Record: The Highest Magnetic Fields Are Created in Dresden On June 22, 2011, the Helmholtz-Zentrum Dresden-Rossendorf set a new world record for magnetic fields with 91.4 Tesla. To reach this record, Sergei Zherlitsyn and his colleagues at the High Magnetic Field Laboratory Dresden (HLD) developed a coil weighing about 200 kilograms in which electric current create the giant magnetic field for a period of a few milliseconds. The coil survived the experiment unscathed. Press release of the Helmholtz-Zentrum Dresden-Rossendorf

Strong exchange and magnetic blocking in N23--radical-bridged lanthanide complexes Single-molecule magnets approach the ultimate size limit for spin-based devices. These complexes can retain spin information over long periods of time at low temperature, suggesting possible applications in high-density information storage, quantum computing and spintronics. Notably, the success of most such applications hinges upon raising the inherent molecular spin-inversion barrier. Although recent advances have shown the viability of lanthanide-containing complexes in generating large barriers, weak or non-existent magnetic exchange coupling allows fast relaxation pathways that mitigate the full potential of these species. In a recent article the authors show that the diffuse spin of an N23--radical bridge can lead to exceptionally strong magnetic exchange in dinuclear Ln(III) (Ln = Gd, Dy) complexes. The Gd(III) congener exhibits the strongest magnetic coupling yet observed for that ion, while incorporation of the high-anisotropy Dy(III) ion gives rise to a molecule with a record magnetic blocking temperature of 8.3 K at a sweep rate of 0.08 T/s. Jeffrey D. Rinehart, Ming Fang, William J. Evans, Jeffrey R. Long, Strong exchange and magnetic blocking in N23--radical-bridged lanthanide complexes, Nature Chemistry (2011) Published online 22 May 2011

Chemical Society Reviews, Themed issue: Molecule-based magnets Guest editors Joel Miller and Dante Gatteschi introduce the molecule-based magnets themed issue of Chemical Society Reviews. With contributions of Gatteschi, Cornia, Sessoli, Winpenny, Meisel, Dunbar, Tsukerblat, Coronado, Verdaguer, Oshio, ... Chemical Society Reviews, Themed issue Molecule-based magnets, Chem. Soc. Rev., 2011, 40, Issue 6

The first magnetization experiment after March 11 from IMR, Tohoku On 26th of April the first low temperature magnetization experiment after the earthquake was performed at the Institute for Materials Research, Tohoku University in collaboration with Leroy Cronin at Glasgow University. The material is newly synthesized clusters with multi-magentic centers. A clear temperature dependence of the hysteresis as well as the clean magnetization curve at 0.5 K exhibit the full recovery of the research. Luckily, no serious damage of the instrument was caused by the earthquake, however, the laboratory has worked carefully to built up the solid safety in the last 45 days. Moreover, some time is needed to exchange the transfer tube of Helium liquefier. Now IMR group declares the restart from the spring break with sincere thanks for all supports given to us in the last several weeks. Recovery reports from the Institute for Materials Research, Tohoku University

Room-Temperature Electrical Addressing of a Bistable Spin-Crossover Molecular System A switchable molecular device is constructed by contacting an individual nanoparticle based on spin-crossover molecules between nanometer-spaced electrodes. The switching and memory effects near room temperature are a consequence of the intrinsic bistability of the nanoparticle. Interestingly, for molecular spintronics, the spin crossover can also be induced by applying a voltage, showing that its magnetic state is electrically controllable. Ferry Prins, Maria Monrabal-Capilla, Edgar A. Osorio, Eugenio Coronado, Herre S. J. van der Zant, Room-Temperature Electrical Addressing of a Bistable Spin-Crossover Molecular System, Advanced Materials, Volume 23, Issue 13, pages 1545-1549 (2011)

A Density-Functional Study of Heterometallic Cr-Based Molecular Rings Density-functional theoretical investigation of the electronic and magnetic properties of octametallic Cr-based molecular antiferromagnetic rings are presented. The presence of the divalent magnetic ion M unbalances the charge and the spin of the parent Cr8 ring, leading to a finite total spin in the molecules. Exchange interaction parameters have been extracted from broken-symmetry calculations and compared with the available experiments; in agreement with them, we find that exchange parameters are rather similar in the two derivatives. The analysis of the electronic properties shows some differences depending on M, in particular in the size of the highest occupied molecular orbital to lowest unoccupied molecular orbital (HOMO-LUMO) gaps. V. Bellini and M. Affronte, A Density-Functional Study of Heterometallic Cr-Based Molecular Rings, J. Phys. Chem. B, 2010, 114 (46), 14797-14806

A Double-Switching Multistable Fe4 Grid Complex with Stepwise Spin-Crossover and Redox Transitions A Fe4 grid complex featuring two orthogonal switching modes, namely stepwise spin-crossover and sequential redox processes, is presented as the cover article of issue 48/2010 of Angewandte Chemie. Of particular interest are the resulting twofold-degenerate configurations [HS-LS-HS-LS] and [FeII2FeIII2], where two identical metal centers occupy opposite corners of the Fe4 square. Such an arrangement qualifies this new grid complex as a potential building block for quantum cellular automata. B. Schneider, S. Demeshko, S. Dechert, F. Meyer, A Double-Switching Multistable Fe4 Grid Complex with Stepwise Spin-Crossover and Redox Transitions, Angew. Chem. 2010, 122, 9461-9464; Angew. Chem. Int. Ed. 2010, 49, 9274-9277.

A New Family of 1D Exchange Biased Heterometal Single-Molecule Magnets: Observation of Pronounced Quantum Tunneling Steps in the Hysteresis Loops of Quasi-Linear {Mn2Ni3} Clusters First members of a new family of heterometallic Mn/Ni complexes [Mn2Ni3X2L4(LH)2(H2O)2] (X = Cl: 1; X = Br: 2) with the new ligand 2-{3-(2-hydroxyphenyl)-1H-pyrazol-1-yl}ethanol (H2L) have been synthesized. The molecular structures feature a quasi-linear Mn-Ni-Ni-Ni-Mn core with six-coordinate metal ions, where elongated axes of all the distorted octahedral coordination polyhedra are aligned parallel and are fixed with respect to each other by intramolecular hydrogen bonds. The compounds exhibit a quite strong ferromagnetic exchange. Slow relaxation of the magnetization at low temperatures and single-molecule magnet (SMM) behavior are evident from frequency-dependent peaks in the out-of-phase ac susceptibilities and magnetization versus dc field measurements, with significant energy barriers to spin reversal Ueff = 27 K (1) and 22 K (2). Pronounced quantum tunnelling steps are observed in the hysteresis loops. Animesh Das, Klaus Gieb, Yulia Krupskaya, Serhiy Demeshko, Sebastian Dechert, Rüdiger Klingeler, Vladislav Kataev, Bernd Büchner, Paul Müller, Franc Meyer, A New Family of 1D Exchange Biased Heterometal Single-Molecule Magnets: Observation of Pronounced Quantum Tunneling Steps in the Hysteresis Loops of Quasi-Linear {Mn2Ni3} Clusters, J. Am. Chem. Soc. (2011)

Tim And The Pan-Galactic Civil Servants "One night Timothy Becket woke to an adventure that would take him beyond his wildest dreams. With the Pan-Galactic Civil Servants - Clarence Smith, Marvelious Fermionus, Coola Baloola, Garvin McGuffin and Colonel Glumm - at his side, Tim must find the all-powerful Cerulean Circlet before the forces of darkness can claim it for their own. Before the Big Bang, the Architects used the Cerulean Circlet to create the Universe. ..." Damian J.J. Farnell, usually known for his scientific contributions to the physics of spin systems (coupled cluster method), invites us to enjoy his first work of fiction. Damian J.J. Farnell, Tim And The Pan-Galactic Civil Servants, CreateSpace, ISBN-10: 1453776303, ISBN-13: 978-1453776308

Rational design of single-molecule magnets: a supramolecular approach Rational design of single-molecule magnets with C3-symmetry is reported in a new Feature Article in the Emerging Investigators issue of Chemical Communications. C3-symmetry minimizes the quantum tunneling of the magnetization through the anisotropy barrier and thus stabilizes the magnetization. Based on a purposely designed triplesalen ligand heptanuclear complexes of the form [Mt6Mc]n+ could be synthesized, among them the isostructural series [MnIII6CrIII]3+, [MnIII6FeIII]3+, and [MnIII6CoIII]3+ with [MnIII6CrIII]3+ being a SMM. A detailed analysis and comparison of the magnetic properties provides significant insight for further optimization of the SMM properties. Thorsten Glaser, Rational design of single-molecule magnets: a supramolecular approach, Chem. Commun., 2011, 47, 116-130

Spin- and Energy-Dependent Tunneling through a Single Molecule with Intramolecular Spatial Resolution The spin- and energy-dependent tunneling through a single organic molecule (CoPc) adsorbed on a ferromagnetic Fe thin film is investigated: spatially resolved by low-temperature spin-polarized scanning tunneling microscopy. Interestingly, the metal ion as well as the organic ligand show a significant spin dependence of tunneling current flow. State-of-the-art DFT calculations including also van der Waals interactions reveal a strong hybridization of molecular orbitals and substrate 3d states. The molecule is anionic due to a transfer of one electron, resulting in a nonmagnetic (S=0) state. Nevertheless, tunneling through the molecule exhibits a pronounced spin dependence due to spin-split molecule-surface hybrid states. Jens Brede, Nicolae Atodiresei, Stefan Kuck, Predrag Lazi, Vasile Caciuc, Yoshitada Morikawa, Germar Hoffmann,Stefan Blügel, and Roland Wiesendanger, Spin- and Energy-Dependent Tunneling through a Single Molecule with Intramolecular Spatial Resolution, Phys. Rev. Lett. 105, 047204 (2010)

X-ray absorption and magnetic circular dichroism investigation of bis(phthalocyaninato)terbium single-molecule magnets deposited on graphite Magnetization as a function of the external field at T=7 K. Bisphthalocyaninato terbium complexes show a long magnetization relaxation time at relatively high temperatures, which makes them very interesting as magnets at single-molecule level. Their technological exploitation, however, requires the addressing of the individual molecules, therefore the deposition of single-molecule magnets on surfaces is a topic of great interest as the interaction with the substrate can play a crucial role in the definition of the molecule properties. In the present work the electronic and magnetic properties of anionic and neutral forms of a bis(phthalocyaninato)terbium derivative deposited on graphite are investigated by means of x-ray absorption spectroscopy and x-ray magnetic circular dichroism. The comparison of the magnetization values and their dependence on the external magnetic field and temperature suggest that the magnetic properties of molecules are preserved when adsorbed onto the graphite surface. R. Biagi, J. Fernandez-Rodriguez, M. Gonidec, A. Mirone, V. Corradini, F. Moro, V. De Renzi, U. del Pennino, J. C. Cezar, D. B. Amabilino, and J. Veciana, X-ray absorption and magnetic circular dichroism investigation of bis(phthalocyaninato)terbium single-molecule magnets deposited on graphite, Phys. Rev. B 82, 224406 (2010)

Probing Superexchange Interaction in Molecular Magnets by Spin-Flip Spectroscopy and Microscopy The superexchange mechanism in cobalt phthalocyanine (CoPc) thin films was studied by a low temperature scanning tunneling microscope. The CoPc molecules were found to form one-dimensional antiferromagnetic chains in the film. Collective spin excitations in individual molecular chains were measured with spin-flip associated inelastic electron tunneling spectroscopy. By spatially mapping the spin-flipping channels with submolecular precision, the authors are able to explicitly identify the specific molecular orbitals that mediate the superexchange interaction between molecules. Xi Chen, Ying-Shuang Fu, Shuai-Hua Ji, Tong Zhang, Peng Cheng, Xu-Cun Ma, Xiao-Long Zou, Wen-Hui Duan, Jin-Feng Jia, and Qi-Kun Xue, Probing Superexchange Interaction in Molecular Magnets by Spin-Flip Spectroscopy and Microscopy, Phys. Rev. Lett. 101, 197208 (2008)

Co-Gd phosphonate complexes as magnetic refrigerants Three 3d-4f phosphonate complexes, [CoII8GdIII8(Ì3-OH)4(NO3)4(O3PtBu)8(O2CtBu)16], [CoII8GdIII4(O3PtBu)6(O2CtBu)16] and [CoII4GdIII6(O3PCH2Ph)6(O2CtBu)14(MeCN)2], have been synthesized and have structures that can be related to molecular grids. Magnetic studies show they have promise as low temperature magnetic refrigerants. See also RCS Publishing, Chemical Science Blog. Yan-Zhen Zheng, Marco Evangelisti and Richard E. P. Winpenny, Co-Gd phosphonate complexes as magnetic refrigerants, Chem. Sci., 2011, 2, 99-102

FIT-MART fits smart The FIT-MART package is a "Fully Integrated Tool for Magnetic Analysis in Research & Teaching" (hence the acronym) which provides a very simple interface for defining complex quantum spin models, carrying out complex calculations, and visualizing the results using several graphical representations. These representations include plots of the energy spectrum as well as plots of the magnetization and magnetic susceptibility as a function of temperature and magnetic field. The FIT-MART package is an Open Source Physics package written to help students as well as researchers who are studying magnetism. It is distributed as a ready-to-run (compiled) Java archive. Larry Engelhardt and Cameron Rainey, FIT-MART package

High-spin ground states via electron delocalization in mixed-valence imidazolate-bridged divanadium complexes Structure of [(PY5Me2)VII(µ-Lbr) VIII(PY5Me2)]4+ Many magnetic molecules rely on the superexchange mechanism. The possibility of instead using a double-exchange mechanism (based on electron delocalization rather than Heisenberg exchange through a non-magnetic bridge) presents a tantalizing prospect for synthesizing molecules with high-spin ground states that are well isolated in energy. In the article it is demonstrated that magnetic double exchange can be sustained by simple imidazolate bridging ligands, known to be well suited for the construction of coordination clusters and solids. A series of mixed-valence vanadium dimers were synthesized and their electron delocalization probed through cyclic voltammetry and spectroelectrochemistry. Magnetic susceptibility data reveal a well-isolated S = 5/2 ground state arising from double exchange. Bettina Bechlars, Deanna M. D'Alessandro, David M. Jenkins, Anthony T. Iavarone, Starla D. Glover, Clifford P. Kubiak, Jeffrey R. Long, High-spin ground states via electron delocalization in mixed-valence imidazolate-bridged divanadium complexes, Nature Chemistry 2, 362 - 368 (2010)

Molecular Magnets themed issue of Dalton Transactions Dalton Trans. 39 (2010) "The study of magnetic cluster complexes, from the fundamental chemistry and physics that governs their properties to their potential applicability in a range of technologies, is a topic that transcends traditional scientific boundaries, with current research producing ground-breaking science. With the Molecular Magnets themed issue, Dalton Transactions continues its efforts in covering all areas represented by the subject including synthesis, structural characterisation, functional properties, physics and materials science, theory and application." Euan K. Brechin Molecular Magnets themed issue, Dalton Trans. 39 (2010)

Review on cobalt(II) single-molecule magnets Structure of [Co4(cit)4]8− This short tutorial review covers recent progress in the field of polynuclear cobalt(II)-based complexes, which display slow magnetic relaxation at low temperature. Cobalt(II) single-molecule magnets (SMMs) can display much larger magnetic anisotropies and hence, potentially higher blocking temperatures than SMMs based on ions where the zero-field splitting originates from a second order spin-orbit coupling, such as manganese(III). Mark Murrie, Cobalt(II) single-molecule magnets, Chem. Soc. Rev., 2010, 39, 1986-1995

Experimental and theoretical investigations of magnetic molecules with non-collinear local d-tensors Mn3Cr: scetch of exchange interactions and directions of local easy axes In spite of its topologically simple magnetic structure, the [CrIIIMnII3 (PyA)6Cl3] (CrMn3) molecule exhibits nontrivial magnetic properties, which emerge from the combined action of single-ion anisotropy and frustration. The present work elucidates the underlying electronic and magnetic properties of the heteronuclear, spin-frustrated CrMn3 molecule by applying X-ray magnetic circular dichroism (XMCD), as well as magnetization measurements in high magnetic fields, density functional theory, ligand-field multiplet calculations as well as quantum and classical spin model calculations. Manuel Prinz, Karsten Kuepper, Christian Taubitz, Michael Raekers, Sumit Khanra, Biplab Biswas, Thomas Weyhermüller, Marc Uhlarz, Joachim Wosnitza, Jürgen Schnack, Andrei V. Postnikov, Christian Schröder, Simon J. George, Manfred Neumann, and Phalguni Chaudhuri, A Star-shaped Heteronuclear CrIIIMnII3 Species and Its Precise Electronic and Magnetic Structure: Spin Frustration Studied by X-ray Spectroscopic, Magnetic and Theoretical Methods, Inorg. Chem. 49 (2010) 2093-2102 V4: anisotropy easy axis and easy planes Magnetic studies of clusters [V4Cl6(thme)2(bipy)3] and related compounds reveal very weak intramolecular antiferromagnetic exchange and very strong local zero-field splitting effects that dominate the magnetization behavior. Ian S. Tidmarsh, Luke J. Batchelor, Emma Scales, Rebecca H. Laye, Lorenzo Sorace, Andrea Caneschi, Jürgen Schnack and Eric J. L. McInnes, Tri-, tetra- and octa-metallic vanadium(III) clusters from new, simple starting materials: interplay of exchange and anisotropy effects, Dalton Trans. (2009) 9402-9409

Co Dimers on Hexagonal Carbon Rings Proposed as Subnanometer Magnetic Storage Bits Magnetic anisotropy energy of Co atoms in different chemical and structural environments. Black squares denote experimental data, blue circles and red diamonds denote lower and upper estimate theoretical data, In the article it is demonstrated by means of density functional and ab initio quantum chemical calculations, that transition-metal-carbon systems have the potential to enhance the presently available area density of magnetic recording by 3 orders of magnitude. As a model system, Co2 benzene with a diameter of 0.5 nm is investigated. It shows a magnetic anisotropy of the order of 0.1 eV per molecule, large enough to store permanently 1 bit of information at temperatures considerably larger than 4 K. A similar performance can be expected, if cobalt dimers are deposited on graphene or on graphite. Xiao, Ruijuan and Fritsch, Daniel and Kuzmin, Michael D. and Koepernik, Klaus and Eschrig, Helmut and Richter, Manuel and Vietze, Knut and Seifert, Gotthard, Co Dimers on Hexagonal Carbon Rings Proposed as Subnanometer Magnetic Storage Bits, Phys. Rev. Lett. 103 (2009) 187201

Electronic Control of Spin Coupling in Keplerate-Type Polyoxomolybdates In the article it could be shown that the partial reduction of polyoxomolybdate building blocks in Keplerate cluster structures allows the magnetic superexchange mediated by these diamagnetic blocks to be altered. The isolation of a 16-fold reduced {Mo72Fe30} species illustrates how Raman-monitored synthesis can result in such clusters comprising a well-defined assembly of spin centers. Bogdan Botar, Arkady Ellern, Raphael Hermann, Paul Kögerler Electronic Control of Spin Coupling in Keplerate-Type Polyoxomolybdates, Angew. Chem. Int. Ed. 2009, 48, 9080-9083

Ab initio investigation of the non-collinear magnetic structure and the lowest magnetic excitations in dysprosium triangles The unusual magnetism exhibited by dysprosium triangles is explained using the recently developed ab initio methodology for the simulation of magnetic properties of complexes. The local anisotropy axes on the dysprosium sites are found to lie in the plane of the Dy3 triangle and to make angles of ca. 120° with each other. The small antiferromagnetic exchange interaction between sites leads to a non-magnetic Kramers doublet in the ground state of the complex. The arrangement of the local magnetization vectors in this state is close to toroidal. By contrast, the lowest excited states are characterized by a huge magnetic moments of ca. 20 Bohr magnetons and show very different behavior of magnetization for fields applied along and perpendicular to the plane of the Dy3 triangle. Liviu Ungur, Willem Van den Heuvel and Liviu F. Chibotaru Ab initio investigation of the non-collinear magnetic structure and the lowest magnetic excitations in dysprosium triangles, New J. Chem., 2009, 33, 1224-1230

Towards odd-membered spin rings Structure of the oxovanadium heptagons sandwiched by beta-cyclodextrins (l.h.s.) and magnetization curves exhibiting characteristic steps (r.h.s.). For a long time it seemed to be practically impossible to synthesize odd-membered spin rings due to steric hindrance of the (bulky) ligands. A recent article reports the successful synthesis and magnetic characterization of a seven-membered vanadium spin ring. Antiferromagnetically coupled odd-membered rings are expected to show a qualitatively different behavior due to spin frustration. For example, the ground state is fourfold degenerate for half-integer spins, but non-degenerate for integer ones, see Ref. Bärwinkel et al.. In the recent investigation the characteristic behavior for the half-integer case was investigated by means of magnetization measurements. Norihisa Hoshino, Motohiro Nakano, Hiroyuki Nojiri, Wolfgang Wernsdorfer, and Hiroki Oshio, Templating Odd Numbered Magnetic Rings: Oxovanadium Heptagons Sandwiched by beta-Cyclodextrins, J. Am. Chem. Soc. 131 (2009) 15100 K. Bärwinkel, P. Hage, H.-J. Schmidt, J. Schnack, Quantum numbers for relative ground states of antiferromagnetic Heisenberg spin rings, Phys. Rev. B 68, 054422 (2003) see also: Hong-Chang Yao, Jun-Jie Wang, Yun-Sheng Ma, Oliver Waldmann, Wen-Xin Du, You Song, Yi-Zhi Li, Li-Min Zheng, Silvio Decurtins and Xin-Quan Xin, An iron(III) phosphonate cluster containing a nonanuclear ring, Chem. Commun. (2006) 1745

Tuning Molecule-Mediated Spin Coupling in Bottom-Up-Fabricated Vanadium-Tetracyanoethylene Nanostructures Highly resolved STM images and structural models of (a) TCNE, (b) V-TCNE, (c) V(TCNE)2, (d) V2TCNE@27°, and (e) V2TCNE@11° on Ag(100). In this article the fabrication of a hybrid magnetic complexes from V atoms and tetracyanoethylene ligands via atomic manipulation with a cryogenic scanning tunneling microscope is reported. Using tunneling spectroscopy one observes spin-polarized molecular orbitals as well as Kondo behavior. For complexes having two V atoms, the Kondo behavior can be quenched for different molecular arrangements, even as the spin-polarized orbitals remain unchanged. This is explained by variable spin-spin (i.e., V-V) ferromagnetic coupling through a single tetracyanoethylene (TCNE) molecule, as supported by density functional calculations. Daniel Wegner and Ryan Yamachika and Xiaowei Zhang and Yayu Wang and Tunna Baruah and Mark R. Pederson and Bart M. Bartlett and Jeffrey R. Long and Michael F. Crommie, Tuning Molecule-Mediated Spin Coupling in Bottom-Up-Fabricated Vanadium-Tetracyanoethylene Nanostructures, Phys. Rev. Lett. 103, 087205 (2009)

Condensed Matter Physics special issue on spin systems Condensed Matter Physics special issue on spin systems, CONDENSED MATTER PHYSICS, 2009, vol. 12, No. 3 Nowadays spin model theory is a very broad field in condensed physics and statistical physics. The Condensed Matter Physics special issue on spin systems touches only upon a small part of the existing studies and by no means exhausts numerous investigations on spin systems. Editor of the issue: O.V. Derzhko

Deutsche Forschungsgemeinschaft Molecular Magnetism Research Report Deutsche Forschungsgemeinschaft Molecular Magnetism Research Report, Coordination Chemistry Reviews, Volume 253, Issues 19-20, Pages 2241-2460 (October 2009) This volume of the Coordination Chemistry Reviews highlights the research results of the German priority program SPP 1137 on Molecular Magnetism (2002-2008) which was a joined effort of chemists and physicists to explore the new and very vivid field of molecular magnetism. The priority program was financed by the Deutsche Forschungsgemeinschaft.

Tailoring the Nature of Magnetic Coupling of Fe-Porphyrin Molecules to Ferromagnetic Substrates We demonstrate that an antiferromagnetic coupling between paramagnetic Fe-porphyrin molecules and ultrathin Co and Ni magnetic films on Cu(100) substrates can be established by an intermediate layer of atomic oxygen. The coupling energies have been determined from the temperature dependence of x-ray magnetic circular dichroism measurements. By density functional theory+U calculations the coupling mechanism is shown to be superexchange between the Fe center of the molecules and Co surface-atoms, mediated by oxygen. M. Bernien, J. Miguel, C. Weis, Md. E. Ali, J. Kurde, B. Krumme, P. M. Panchmatia, B. Sanyal, M. Piantek, P. Srivastava, K. Baberschke, P. M. Oppeneer, O. Eriksson, W. Kuch, and H. Wende, Tailoring the Nature of Magnetic Coupling of Fe-Porphyrin Molecules to Ferromagnetic Substrates, Phys. Rev. Lett. 102, 047202 (2009)

Microscopic Understanding of Negative Magnetization in Cu, Mn, and Fe Based Prussian Blue Analogues Rietveld refined neutron diffraction pattern for Cu0.73Mn0.77[Fe(CN)6]·zH2O at room temperature. A crossover of the field-cooled magnetization from positive to negative has been observed below the magnetic ordering temperature (17.9 K) in a multimetal Prussian Blue analogue (PBA), Cu0.73Mn0.77[Fe(CN)6]·zH2O. The reverse Monte Carlo (RMC) modeling (using the program RMCPOW) has been used to derive the various scattering contributions (e.g., nuclear diffuse, nuclear Bragg, magnetic diffuse, and magnetic Bragg) from the observed neutron diffraction patterns. The RMC analysis combined with the Rietveld refinement technique show an antiferromagnetic ordering of Mn moments with respect to the Cu as well as the Fe moments. Our study gives the first neutron magnetic structure evidence towards the microscopic understanding of the negative magnetization in the PBAs. Amit Kumar, S. M. Yusuf, L. Keller, and J. V. Yakhmi, Microscopic Understanding of Negative Magnetization in Cu, Mn, and Fe Based Prussian Blue Analogues, Phys. Rev. Lett. 101, 207206 (2008)

Maximum use of symmetry For small enough quantum systems numerical exact and complete diagonalization of the Hamiltonian enables one to evaluate and discuss all static, dynamic, and thermodynamic properties. In a recent article the range of applicability of the exact diagonalization method for Heisenberg spin systems is extend by showing how the irreducible tensor operator technique can be combined with an unrestricted use of general point-group symmetries. Results for numerical exact diagonalizations of Heisenberg spin systems of unprecedented size are presented as e.g. for the antiferromagnetic cuboctahedron with total Hilbert space dimension is 16,777,216. Low-lying energy spectrum of the antiferromagnetic cuboctahedron with s=3/2 in subspaces of S=0,1,2,3. Symbols denote the irreducible representations of the Oh group. R. Schnalle, J. Schnack, Numerically exact and approximate determination of energy eigenvalues for antiferromagnetic molecules using irreducible tensor operators and general point-group symmetries, Phys. Rev. B 79 (2009) 104419 Also in this work, the spin system consisting of four Ni ions (s=1) was analyzed by making massive use of symmetries. Especially it is shown that in the molecular Ni4 clusters with S4 symmetry, not only the local anisotropy but also the antisymmetric exchange interaction contributes to the observed fourth-order anisotropy terms in the single-spin Hamiltonian. N. Kirchner, J. van Slageren, B. Tsukerblat, O. Waldmann, M. Dressel, Antisymmetric exchange interactions in Ni4 clusters, Phys. Rev. B 78, 094426 (2008)

Engineering the coupling between molecular spin qubits by coordination chemistry The ability to assemble weakly interacting subsystems is a prerequisite for implementing quantum information processing and generating controlled entanglement. In a new article it is shown that Cr7Ni rings can be chemically linked to each other and that the coupling between their spins can be tuned by choosing the linker. Calculations that demonstrate how realistic microwave pulse sequences could be used to generate maximally entangled states in such molecules are presented. Grigore A. Timco, Stefano Carretta, Filippo Troiani, Floriana Tuna, Robin J. Pritchard, Christopher A. Muryn, Eric J. L. McInnes, Alberto Ghirri, Andrea Candini, Paolo Santini, Giuseppe Amoretti, Marco Affronte, Richard E. P. Winpenny, Engineering the coupling between molecular spin qubits by coordination chemistry, Nature Nanotechnology, Published online: 01 February 2009;

Magnetic memory of a single-molecule quantum magnet wired to a gold surface In the field of molecular spintronics the use of magnetic molecules for information technology is a main target and the observation of magnetic hysteresis on individual molecules organized on surfaces is a necessary step to develop molecular memory arrays. So far no magnetic hysteresis has been reported for monolayers of SMMs on various non-magnetic substrates, most probably owing to the chemical instability of clusters on surfaces. Using X-ray absorption spectroscopy and X-ray magnetic circular dichroism synchrotron-based techniques, pushed to the limits in sensitivity and operated at sub-kelvin temperatures, it has been found that robust, tailor-made Fe4 complexes retain magnetic hysteresis at gold surfaces. Matteo Mannini, Francesco Pineider, Philippe Sainctavit, Chiara Danieli, Edwige Otero, Corrado Sciancalepore, Anna Maria Talarico, Marie-Anne Arrio, Andrea Cornia, Dante Gatteschi, Roberta Sessoli, Magnetic memory of a single-molecule quantum magnet wired to a gold surface, Nature Materials 8, 194 - 197 (2009) See also News and Views: Heiko Wende, Molecular magnets: How a nightmare turns into a vision, Nature Materials 8, 165 - 166 (2009)

Landing a manganese cluster on a POM The functionalization of a pre-formed, high oxidation state {CeIVMnIV6} cluster with a lacunary phosphotungstate, [Alpha-P2W15O56]12-, exemplifies a straightforward route for grafting redox-active building blocks to existing Mn-carboxylate clusters and modeling their deposition onto metal oxide surfaces. Xikui Fang and Paul Kögerler, A polyoxometalate-based manganese carboxylate cluster, Chem. Commun., 2008, 3396 - 3398

New polyoxometalates Several new polyoxomatelate cluster could be synthesized. Among them are octa- and nonanuclear nickel(II) polyoxometalate clusters and a 16-Metal-Centre Iron Oxide Nanocluster that is the result of anucleation process in the Cavity of a 48-Tungstophosphate Wheel. Another cluster that contains a Cu3 spin triangle was investigated in detail using pulsed-field magnetization, electron spin resonance, and nuclear spin-lattice relaxation. The latter compound shows an unusual hysteresis loop. Pichon, Celine; Mialane, Pierre; Dolbecq, Anne; Marrot, Jerome; Riviere, Eric; Bassil, Bassem; Kortz, Ulrich; Keita, Bineta; Nadjo, Louis; Secheresse, Francis, Octa- and Nonanuclear Nickel(II) Polyoxometalate Clusters: Synthesis and Electrochemical and Magnetic Characterizations Inorg. Chem., 2008, 47 (23), pp 11120-11128 Mal, Sib Sankar; Dickman, Michael H.; Kortz, Ulrich; Todea, Ana Maria; Merca, Alice; Boegge, Hartmut; Glaser, Thorsten; Mueller, Achim; Nellutla, Saritha; Kaur, Narpinder; van Tol, Johan; Dalal, Naresh S.; Keita, Bineta; Nadjo, Louis, Nucleation Process in the Cavity of a 48-Tungstophosphate Wheel Resulting in a 16-Metal-Centre Iron Oxide Nanocluster Chem. Eur. J. 2008, 14, 1186-1195 Kwang-Yong Choi and Naresh S. Dalal and Arneil P. Reyes and Philip L. Kuhns and Yasuhiro H. Matsuda and Hiroyuki Nojiri and Sib Sankar Mal and Ulrich Kortz, Pulsed-field magnetization, electron spin resonance, and nuclear spin-lattice relaxation in the {Cu3} spin triangle Phys. Rev. B 77, 024406 (2008)

Visualizing the Spin of Individual Cobalt-Phthalocyanine Molecules CoPc molecules adsorbed on cobalt nanoislands grown on Cu(111). Low-temperature spin-polarized scanning tunneling microscopy is employed to study spin transport across single cobalt-phthalocyanine molecules adsorbed on well-characterized magnetic nanoleads. A spin-polarized electronic resonance is identified over the center of the molecule and exploited to spatially resolve stationary spin states. These states reflect two molecular spin orientations and, as established by density functional calculations, originate from a ferromagnetic molecule-lead exchange interaction. C. Iacovita, M. V. Rastei, B. W. Heinrich, T. Brumme, J. Kortus, L. Limot, and J. P. Bucher Visualizing the Spin of Individual Cobalt-Phthalocyanine Molecules, Phys. Rev. Lett. 101, 116602 (2008)

Direct Observation of Quantum Coherence in Single-Molecule Magnets Rabi oscillations obtained by recording the echo intensity as a function of nutation pulse length. For two positions in the Rabi cycle the corresponding path on the Bloch sphere is shown on the right. Direct evidence of quantum coherence in a single-molecule magnet in a frozen solution is reported with coherence times as long as T2=630±30 ns. We can strongly increase the coherence time by modifying the matrix in which the single-molecule magnets are embedded. The electron spins are coupled to the proton nuclear spins of both the molecule itself and, interestingly, also to those of the solvent. The clear observation of Rabi oscillations indicates that we can manipulate the spin coherently, an essential prerequisite for performing quantum computations. C. Schlegel, J. van Slageren, M. Manoli, E. K. Brechin, and M. Dressel, Direct Observation of Quantum Coherence in Single-Molecule Magnets, Phys. Rev. Lett. 101, 147203 (2008)

Spin Chirality in a Molecular Dysprosium Triangle: the Archetype of the Non-Collinear Ising Model Molecular nanomagnetism has provided benchmark systems to investigate new and fascinating phenomena in magnetism like magnetic memory at the molecular level, quantum tunneling of the magnetization or destructive interferences in the tunneling pathways. In this field rare earth ions like dysprosium(III) are currently investigated because of their large magnetic anisotropy. In the course of our synthetic efforts to obtain new molecular nanomagnets we recently obtained trinuclear DyIII clusters with almost ideal trigonal symmetry but with the unusual property of possessing a non magnetic ground state. Cancellation of the magnetic moments, resulting in a non-magnetic ground doublet, originates from the non-collinearity of the single ion easy axes of magnetization, as demonstrated by single crystal magnetic studies. The peculiar chiral nature of the ground non-magnetic doublet and the resonant quantum tunneling of the magnetization at the crossings of the discrete energy levels open new perspectives in quantum computation and data storage in molecular nanomagnets. Structure of the Dy3 cluster and its low energy levels as a function of the applied magnetic field. Below 8 kOe two degenerate non magnetic states with opposite spin chirality have the lowest energy. J. Luzon, K. Bernot, I. J. Hewitt, C. E. Anson, A. K. Powell, and R. Sessoli, Spin Chirality in a Molecular Dysprosium Triangle: the Archetype of the Non-Collinear Ising Model, Phys. Rev. Lett. 100, 247205 (2008)

Strong magneto-chiral dichroism in enantiopure chiral ferromagnets Temperature dependence of the MChD effect (diamonds) measured at 615 nm and field-cooled (squares) magnetization. As materials science is moving towards the synthesis, the study and the processing of new materials exhibiting well-defined and complex functions, the synthesis of new multifunctional materials is one of the important challenges. One of these complex physical properties is magneto-chiral dichroism which arises, at second order, from the coexistence of spatial asymmetry and magnetization in a material. Recently the first measurement of strong magneto-chiral dichroism in an enantiopure chiral ferromagnet was reported. The ab initio synthesis of the enantiopure chiral ferromagnet is based on an enantioselective self-assembly, where a resolved chiral quaternary ammonium cation imposes the absolute configurations of the metal centres within chromium–manganese two-dimensional oxalate layers. The ferromagnetic interaction between Cr(III) and Mn(II) ions leads to a Curie temperature of 7 K. The magneto-chiral dichroic effect is enhanced by a factor of 17 when entering into the ferromagnetic phase. Cyrille Train, Ruxandra Gheorghe, Vojislav Krstic, Lise-Marie Chamoreau, Nikolai S. Ovanesyan, Geert L. J. A. Rikken, Michel Gruselle, Michel Verdaguer, Strong magneto-chiral dichroism in enantiopure chiral ferromagnets, Nature Materials 7, 729 - 734 (2008)

Observation of a quantum phase transition in a molecular scale transistor Atomic Force Microscope image of the molecular transistor. The inset represents a x100 zoom view of the inserted C60 molecule. As physical objects become smaller, quantum effects become dominant and easier to measure. Thus, nanometer size quantum objects (in this work a C60 molecule) are propitious for observation of the new quantum phenomena associated with spin electronics. Such objects act as artificial atoms and can be controlled by external parameters such as magnetic field, electric potential or light. We have shown that a molecular transistor based on fullerene (C60) can be switched electrostatically between two different spin states, corresponding to distinct resistance properties of the nanocircuit. In this case, the magnetized state is associated with an entanglement of the spin of the molecule with the conduction electron spins. An electrostatic coupling induces the transition from a spin zero state to a spin 1/2 state. The quantum critical point is then characterized by a spin1/2 that is not entangled with the conduction electrons. This kind of physics is of great current interest and, in addition, our experimental results offer new possibilities for controlling and manipulating the states in molecular spintronics. N. Roch, S. Florens, V. Bouchiat, W. Wernsdorfer and F. Balestro, Quantum phase transition in a single-molecule quantum dot, Nature, 453, 633 (2008)

Calculation of the Zero-Field Splitting Tensor Prof. Dr. Frank Neese receives this year's Klung-Wilhelmy-Weberbank prize for chemistry. He receives the prize for his pioneering work on electronic structure calculations for (magnetic) molecules. We would like to highlight some of his recent results especially on the evaluation of zero-field splitting tensors. The zero-field splitting (ZFS) (expressed in terms of the D tensor) is the leading spin-Hamiltonian parameter for systems with a ground state spin S>1/2. To first order in perturbation theory, the ZFS arises from the direct spin-spin dipole-dipole interaction. To second order, contributions arise from spin-orbit coupling (SOC). The latter contributions are difficult to treat since the SOC mixes states of different multiplicities. This is an aspect of dominant importance for the correct prediction of the D tensor. In Frank Neese's work, the theory of the D tensor is discussed from the point of view of analytic derivative theory. F. Neese, Calculation of the Zero-Field Splitting Tensor Using Hybrid Density Functional and Hartree-Fock Theory, J. Chem. Phys. 127 (2007) 164112 Dmitry Ganyushin and F. Neese, First-principles calculations of zero-field splitting parameters, J. Chem. Phys. 125 (2006) 024103 F. Neese, Importance of Direct Spin-Spin Coupling and Spin-Flip Excitations for the Zero-Field Splittings of Transition Metal Complexes: A Case Study, J. Am. Chem. Soc. 128 (2006) 10213-10222

Polyoxometalate-Mediated Self-Assembly of Single-Molecule Magnets The first two examples of MnII/III-based Single Molecule Magnets (SMMs) encapsulated within a polyoxometalate ligand system are reported. These clusters both contain a central, mixed-valence {Mn6} cluster core that is anchored between two rigid lacunary polyoxometalate clusters. Chris Ritchie, Alan Ferguson, Hiroyuki Nojiri, Haralampos N. Miras, Yu-Fei Song, De-Liang Long, Eric Burkholder, Mark Murrie, Paul Kögerler, Euan K. Brechin, Leroy Cronin, Polyoxometalate-Mediated Self-Assembly of Single-Molecule Magnets: {[XW9O34]2[MnIII4MnII2O4(H2O)4]}12-, Angewandte Chemie International Edition 47 (2008) 5609

Quantum oscillations in a molecular magnet The observation and analysis of Rabi oscillations (quantum oscillations resulting from the coherent absorption and emission of photons driven by an electromagnetic wave) of the molecular magnet "V15" in a hybrid system, in which discrete and well-separated magnetic clusters are embedded in a self-organized non-magnetic environment. Each cluster contains 15 antiferromagnetically coupled S = 1/2 spins, leading to an S = 1/2 collective ground state. When this system is placed into a resonant cavity, the microwave field induces oscillatory transitions between the ground and excited collective spin states, indicative of long-lived quantum coherence. The present observation of quantum oscillations suggests that low-dimension self-organized qubit networks having coherence times of the order of 100 micro seconds (at liquid helium temperatures) are a realistic prospect. S. Bertaina, S. Gambarelli, T. Mitra, B. Tsukerblat, A. Müller, B. Barbara, Quantum oscillations in a molecular magnet, Nature 453, 203-206 (8 May 2008)

A star-shaped manganese-based molecule an S = 10 high-spin state A comprehensive study of the electronic and magnetic properties of a star-shaped molecule comprising a MnII4O6 core is reported. One feature of this compound is weak magnetic coupling constants compared to other similar polyoxo compounds. This leads to complicated low-lying magnetic states in which the ground state is not well separated from the upper-lying states, yielding a high-spin molecule with a giant magnetic moment of up to 20 μB/formula unit. Sumit Khanra, Karsten Kuepper, Thomas Weyhermüller, Manuel Prinz, Michael Raekers, Sebastian Voget, Andrei V. Postnikov, Frank M. F. de Groot, Simon J. George, Marin Coldea, Manfred Neumann, and Phalguni Chaudhuri, Star-Shaped Molecule of MnII4O6 Core with an St = 10 High-Spin State. A Theoretical and Experimental Study with XPS, XMCD, and Other Magnetic Methods, Inorg. Chem. 7 (11), 4605-4617 (2008)

Ground state tuning by high magnetic fields in Ni-compounds An important property of a molecular magnet is the possibility to tune its spin state by an external parameter such as the magnetic field. To address this issue we have measured electron spin resonance (ESR) and magnetization in fields up to 55 T of the novel multicenter complex [L2Ni4(N3)O2CAda)4(ClO4)] (a) and the S = 1 two leg spin ladder [Na2Ni2(C2O4)3(H2O)2] (b). Both complexes show a non-magnetic ground state. However, by applicaton of a strong external magnetic field, H > Hc we can turn the ground state to a strongly magnetic one. At Hc the S = 0 singlet is crossed by the excited |S = 1, Sz = -1> spin state. From ESR and magnetization we find that the critical field Hc at which the spin-level crossings occur are at Hc=25 T in (a), Hc=30 T in (b). Furthermore, appreciable zero-field splittings have been observed which are due to the large single-ion anisotropy (11.5 K (a) and -4.8 K (b)) of nickel. C. Golze , A. Alfonsov, R. Klingeler, B. Büchner, V. Kataev , C. Mennerich, H.-H. Klauss, M. Goiran, J.-M. Broto, H. Rakoto, S. Demeshko, G. Leibeling and F. Meyer, Tuning the Magnetic Ground State of a Tetranuclear Nickel(II) Molecular Complex by High Magnetic Fields, Phys. Rev. B 73 (2006) 224403 C. Mennerich, H.-H. Klauss, M. Broekelmann, F. J. Litterst, C. Golze, R. Klingeler, V. Kataev, B. Büchner, S.-N. Grossjohann W. Brenig, M. Goiran, H. Rakoto, J.-M. Broto, O. Kataeva and D.-J. Price, AFM Dimers of Ni(II) in the S = 1 Spin-Ladder Na2Ni2(C2O4)3(H2O)2, Phys. Rev. B 73 (2006) 104415 S. Demeshko, G. Leibeling, W. Maringgele, F. Meyer, C. Mennerich, H.-H. Klauss, and H. Pritzkow. Structural Variety and Magnetic Properties of Tetranuclear Nickel(II) Complexes with a Central μ4-azide. Inorg. Chem. 44, 519 (2005). D. J. Price, A.K. Powell, and P. T. Wood, A new series of layered transition metal oxalates: Hydrothermal synthesis, structural and magnetic properties. J. Chem. Soc., Dalton Trans., 2478-2482 (2003).

Magnetocaloric properties of frustrated antiferromagnetic molecules and low-dimensional spin systems Antiferromagnetically coupled low-dimensional spin systems showing geometric frustration like the sawtooth chain and the kagome lattice as well as frustrated antiferromagnetic molecules have been investigated with respect to their magnetocaloric properties recently. A key feature is the remarkably large adiabatic cooling rate close to the saturation field as shown in the figure for the example of an antiferromagnetic icosahedron. J. Schnack, R. Schmidt, J. Richter, Enhanced magnetocaloric effect in frustrated magnetic molecules with icosahedral symmetry, Phys. Rev. B 76 (2007) 054413 O. Derzhko and J. Richter, Finite low-temperature entropy of some strongly frustrated quantum spin lattices in the vicinity of the saturation field, Phys. Rev. B 70 (2004) 104415 A. Honecker and J. Richter, Entropy of fermionic models on highly frustrated lattices, Condens. Matter Phys. 8, 813 (2005) M.E. Zhitomirsky, A. Honecker, Magnetocaloric Effect in One-Dimensional Antiferromagnets, J. Stat. Mech.: Theor. Exp. (2004) P07012

Density functional studies of molecular magnets After a general introduction into the field of molecular magnets the discussion focuses on a more specific description of their most important representative species, single-molecule magnets incorporating transition metal ions. We overview traditional model approaches for the phenomenological description of such systems and outline some ways used to parameterize the corresponding models from experiment and from first-principle calculations. The latter can be either multi-determinantal quantum chemical schemes or those based on the density functional theory. In particular we discuss Heisenberg exchange parameters and magnetic anisotropy constants. As a practical example, an introduction into problems and properties of some single-molecule magnets which gained much attention within last years, namely Mn12-acetate, Fe8 and V15 systems, is given. This introduction into systems is followed by a critical comparison of calculation schemes based on the density functional theory that are particularly well suited for the study of molecular magnets. For the above systems we select some benchmark results, obtained by different methods. Finally, we outline our recent progress in the study of other single-molecule magnets, including six-membered "ferric wheels", "ferric stars" and "Ni4" molecules, which we studied with the use of firstprinciples methods SIESTA and NRLMOL. Andrei V. Postnikov, Jens Kortus, Mark R. Pederson, Density functional studies of molecular magnets, physica status solidi (b) 243, 2533-2572 (2006)

A Ferromagnetically Coupled Mn19 Aggregate with a Record S=83/2 Ground Spin State We report on the realization of the maximum-spin ground state of 83/2 for a Mn ixed-valence compound. The combination of using an organic ligand which can bridge to multiple metal centers and using azido ligands has resulted in a Mn19 aggregate that exhibits dominant ferromagnetic interactions with the maximum-spin ground state possible. Achieving such a high ground spin state is clearly one of the elusive goals in the search for obtaining superior SMMs. However, although the MnIII centers in the compound show a high degree of Jahn-Teller distortion, their geometrical arrangement and the strong ferromagnetic interactions between spin carriers lead to a system with a very low anisotropy. The challenge now is to find a means of introducing not only maximum spin but also greater anisotropy. Ayuk M. Ako, Ian J. Hewitt, Valeriu Mereacre, Rodolphe Clerac, Wolfgang Wernsdorfer, Christopher E. Anson, Annie K. Powell, Magnetic relaxation studies on a single-molecule magnet by time-resolved inelastic neutron scattering, Angew. Chem. Int. Ed. 45 (2006) 4926-4929

Magnetic relaxation studies on a single-molecule magnet by time-resolved inelastic neutron scattering Time-resolved inelastic neutron scattering measurements on an array of single-crystals of the single-molecule magnet Mn12ac are presented. The data facilitate a spectroscopic investigation of the slow relaxation of the magnetization in this compound in the time domain. O. Waldmann, G. Carver, C. Dobe, D. Biner, A. Sieber, H. U. Güdel, H. Mutka, J. Ollivier, and N. E. Chakov, Magnetic relaxation studies on a single-molecule magnet by time-resolved inelastic neutron scattering, Appl. Phys. Lett. 88 (2006) 042507

Field-Induced Magnetoelastic Instabilities in Antiferromagnetic Molecular Wheels The magnetic torque of the antiferromagnetic molecular wheel CsFe8 was studied down to 50 mK and up to 28 T. Below about 0.5 K phase transitions were observed at the field-induced level crossings (LCs). Intermolecular magnetic interactions are very weak excluding field-induced magnetic ordering. A magnetoelastic coupling was considered. A generic model shows that the wheel structure is unconditionally unstable at the LCs, and the predicted torque curves explain the essential features of the data well. Figure: (a) dtau/dB at the first LC for a single crystal of compound 1 for several temperatures from 55 mK to 1 K. (b) B-T phase diagram as derived from the data shown in panel (a) (lines are guides to the eyes). The solid symbols indicate the critical fields, the open symbols the half-maximum fields for T >T_c. The dashed line indicates the field of the S=0 to S=1 LC. The dash-dotted lines indicate the halfmaximum fields as expected for thermal broadening. O. Waldmann, C. Dobe, T. Ochsenbein, H. U. Güdel,and I. Sheikin, Field-Induced Magnetoelastic Instabilities in Antiferromagnetic Molecular Wheels, Phys. Rev. Lett. 96 (2006) 027206 Please see also: Johannes Richter, Oleg Derzhko, and Jörg Schulenburg, Magnetic-field induced spin-Peierls instability in strongly frustrated quantum spin lattices, Phys. Rev. Lett. 93, 107206 (2004)

Addressing the Metal Centers of [2x2] CoII4 Grid-Type Complexes by STM/STS In their Communication the authors describe the spectroscopic dissecting of a single molecular square into regions of different electronic properties by STM/STS techniques. Figure: a) DFT calculation of occupied orbitals within an energy window between EF and -0.7 eV and the electron density map in superposition with the crystal structure data. b) 3D representation of DFT-calculated electron density maps within an energy window between EF and -0.55 eV and between EF and -1 eV (upper row). Lower row: Central section of the measured CITS maps of Figure. Mohammad Sahabul Alam, Stefan Strömsdörfer, Viacheslav Dremov, Paul Müller, Jens Kortus, Mario Ruben, Jean-Marie Lehn, Addressing the Metal Centers of [2x2] CoII4 Grid-Type Complexes by STM/STS, Angewandte Chemie International Edition, Volume 44, Issue 48 , Pages 7896 - 7900 (2005)

[{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20]36?: A molecular quantum spin icosidodecahedron Self-assembly of aqueous solutions of molybdate and vanadate under reducing, mildly acidic conditions results in a polyoxomolybdate-based {Mo72V30} cluster compound Na8K16(VO)(H2O)5[K10{(Mo)Mo5O21(H2O)3(SO4)}12 (VO)30(H2O)20] *150H2O, a quantum spin-based Keplerate structure. Bogdan Botar, Paul Kögerler, and Craig L. Hill, [{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20]36-: A molecular quantum spin icosidodecahedron, Chem. Commun. 2005, 3138-3140 (2002)

The inverse Landau-Zener-Problem When applying a magnetic field sweep that is linear in time to a two-level system the probability to tunnel can be evaluated according to the works of Landau, Zener, Stueckelberg, and Majorana. But what if one woulkd like to reverse the problem, i.e. how should the functional form of a field sweep W(t) look like in order to obtain a desired tunneling probability function p(t)? This problem was solved theoretically by D.A. Garanin and R. Schilling and awaits its experimental verification. D.A. Garanin and R. Schilling, Inverse problem for the Landau-Zener effect, Europhys. Lett. 59, 7 (2002) D.A. Garanin and R. Schilling, Effects of nonlinear sweep in the Landau-Zener-Stueckelberg effect, Phys. Rev. B 66, 174438 (2002)

Hysteretic Magnetic Bistability Based on a Molecular Azide Switch Like a molecular toggle switch, the bridging azide ion in a highly preorganized dinickel(II) complex turns strong antiferromagnetic coupling on or off. Single crystals of the compound stay intact over the entire temperature range studied and feature hysteretic magnetic bistability not far from ambient temperature. Guido Leibeling, Serhiy Demeshko, Sebastian Dechert, Franc Meyer, Hysteretic Magnetic Bistability Based on a Molecular Azide Switch, Angew. Chem. 2005, 117, 7273-7276; Angew. Chem. Int. Ed. 2005, 44, 7111-7114.

Anions get wheely big A Cu20-containing polyoxotungstate of large size and high symmetry was synthesized by making use of the template effect. The wheel-shaped [Cu20Cl(OH)24(H2O)12(P8W48O184)]25- ion (see picture; black W, turquoise Cu, yellow P, violet Cl, red O) is the first transition-metal-substituted derivative of [H7P8W48O184]33- and incorporates more paramagnetic 3d metal ions than any other polyoxotungstate to date. Sib Sankar Mal and Ulrich Kortz, The Wheel-Shaped Cu20 Tungstophosphate [Cu20Cl(OH)24(H2O)12(P8W48O184)]25- Ion, Angew. Chem. Int. Ed., 44 (2005) 3777-3780

Terahertz Faraday Effect in Single Molecule Magnets For the first time, Faraday rotation in the terahertz frequency range was observed in molecular magnetic systems. The effect is strongest near the magnetic resonance of the single molecule magnet Mn12Ac at ν = 300 GHz, where the Faraday rotation exceeds 150°/mm. Below the magnetization blocking temperature, the effect was observed in the magnetized state of the sample in zero field. Surprisingly, it could even be detected in nonmagnetized states, applying small magnetic fields (H ≤ 1 T), that do not create net magnetization of the sample. All observations were quantitatively explained without fit procedures using known Mn12Ac spin-Hamiltonian parameters. Figure: (top) Transmission spectrum recorded on a single crystal mosaic of Mn12Ac at T = 1.77 K. (middle) radiation ellipticities calculated from angle dependent measurements (c) Faraday rotation angle calculated from angle dependent measurements J. van Slageren, S. Vongtragool, A. Mukhin, B. Gorshunov, M. Dressel, Terahertz Faraday Effect in Single Molecule Magnets, Phys. Rev. B. 72 (2005) 020401R

Néel-Vector Tunneling in Antiferromagnetic Molecular Clusters From inelastic neutron scattering experiments quantum tunneling of the Néel vector in the antiferromagnetic molecular ferric wheel CsFe8 is demonstrated. Analysis of the linewidth of the tunneling transition evidences coherent tunneling. Figure: (a) Crystal structure of CsFe8, (b) Classical ground state spin configuration for the two orientations of the Néel vector. (c) Low-lying energy spectrum. At small anisotropies the levels can be classified by quantum numbers S and M (blue shading). For large anisotropy S looses its significance, but M remains a good quantum number (green shading). This is the region of Néel-vector tunneling. O. Waldmann, C. Dobe, H. Mutka, A. Furrer, and H. U. Güdel, Néel-Vector Tunneling in Antiferromagnetic Molecular Clusters, Phys. Rev. Lett. 95 (2005) 057202

[V30Mo72]: Quantum Keplerate Adding vanadyl sulfate to an acidified molybdate solution, in presence of K+ cations, results in formation of the compound abbreviated as [V30Mo72]. The vanadyl ions form a slightly distorted icosadodecahedron. This fascinating, highly symmetric structure is a spherical arrangement of pentagons and triangles. The S = 1/2 vanadyl ions are strongly exchange coupled. Quantum Monte Carlo simulations show that the average interaction is around J = 245 K. Strong exchange interactions between vanadyl ions despite long exchange pathways is a phenomenon that has been found in other vanadyl polyoxomolybdates. It is much stronger than the exchange interaction in [Fe30Mo72]. The higher spin of the iron ions (S = 5/2) compared to vanadium allowed the application of various classical calculation methods in that case. In that sense [V30Mo72] can be compared as the quantum analogue of [Fe30Mo72] Figure: (top) Combined polyhedral and ball-and-stick representation of the structure of [V30Mo72], showing the triangles and pentagons of the icosidodecahedron, and additionally the basic {VO5} and {VO6} units as green polyhedra; (Mo atoms blue, O atoms red, K atoms purple, and SO42- groups yellow tetrahedra, disordered S atoms yellow). A. Müller, A.M. Todea, M. Dressel, J. van Slageren, H. Bögge, M. Schmidtmann, M. Luban, L. Engelhardt, M. Rusu, On Triangular Geometrical and Magnetic Motifs Uniquely Linked on a Spherical Capsule-Surface, Angew. Chem. Int. Ed. 44 (2005) 3857 - 3861

Fast switching of bistable magnets The use of magnetic nanowires as memory units is made possible by the exponential divergence of the characteristic time for magnetization reversal at low temperature, but the slow relaxation makes the manipulation of the frozen magnetic states difficult. We suggest that finite-size segments can show a fast switching if collective reversal of the spins is taken into account. This mechanism gives rise at low temperatures to a scaling law for the dynamic susceptibility that has been experimentally observed for the dilute molecular chain Co(hfac)2NitPhOMe. These results suggest a possible way of engineering nanowires for fast switching of the magnetization. Alessandro Vindigni, Angelo Rettori, Lapo Bogani, Andrea Caneschi, Dante Gatteschi, Roberta Sessoli, and Miguel A. Novak, Fast switching of bistable magnetic nanowires through collective spin reversal, Appl. Phys. Lett. 87 (2005) 073102

Hysteresis without anisotropy Normally hysteretic behaviour of magnetic systems is the outcome of anisotropic terms in the Hamiltonian. In a recent work we could show that the classical Heisenberg icosahedral antiferromagnet exhibits a hysteresis loop when the external field is swept (see figure). In this hypothetical magnetic molecule the spins are mounted at the vertices of an icosahedron and interact solely via antiferromagnetic nearest neighbor coupling. In the corresponding quantum system the (T=0) magnetization curve exhibits anusual jumps. The whole behavior can be charcterized as a first order metamagnetic phase transition. C. Schröder, H.-J. Schmidt, J. Schnack, and M. Luban, Metamagnetic phase transition of the antiferromagnetic Heisenberg icosahedron, Phys. Rev. Lett. 94 (2005) 207203

Competing Spin Phases in Fe30 Frustrated spin systems such as the kagome lattice antiferromagnet show a pronounced (T=0) magnetization plateau at one third saturation magnetization. Since the magnetic molecule Fe30 is built of spins mounted at the vertices of a perfect icosidodecahedron it is structurally a "little brother" of the kagome antiferromagnet and shares several properties. In a recent experiment we could show that the differential suscptibility dM/dB features a pronounced minimum around one third of the saturation field which gives clear evidence that in this zero-dimensional system the related plateau is produced by competing spin phases just in the same way as on the two-dimensional kagome lattice. C. Schröder, H. Nojiri, J. Schnack, P. Hage, M. Luban, P. Kögerler, Competing Spin Phases in Geometrically Frustrated Magnetic Molecules, Phys. Rev. Lett. 94 (2005) 017205

Giant magnetization jumps For a class of frustrated spin lattices including the Kagome lattice we construct exact eigenstates consisting of several independent, localized one-magnon states and argue that they are ground states for high magnetic fields. If the maximal number of local magnons scales with the number of spins in the system, which is the case for the Kagome lattice, the effect persists in the thermodynamic limit and gives rise to a macroscopic jump in the zero-temperature magnetization curve just below the saturation field. The effect decreases with increasing spin quantum number and vanishes in the classical limit. Thus it is a true macroscopic quantum effect. J. Schulenburg, A. Honecker, J. Schnack, J. Richter, H.-J. Schmidt, Macroscopic magnetization jumps due to independent magnons in frustrated quantum spin lattices, Phys. Rev. Lett. 88 (2002) 167207