Supramolecular aggregates of single-molecule magnets: exchange-biased quantum tunneling of magnetization in a rectangular [Mn<sub>3</sub>]<sub>4</sub> tetramer

Nguyen, Tu N.; Wernsdorfer, Wolfgang; Shiddiq, Muhandis; Abboud, Khalil A.; Hill, Stephen; Christou, George

doi:10.1039/c5sc02599k

Cited by 49 publications

(36 citation statements)

References 105 publications

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“…Ferromagnetic couplings between the MBBs suppress the thermally independent relaxation pathways. Such behavior has been observed in the past for, among others, antiferromagnetically interacting Mn 4 complexes, ferromagnetically coupled Fe 4 supramolecular chains, cyanide‐based SMMs, Dy radical tetramers, Dy III dimers but, to the best of our knowledge, never for 4f chains.…”

Section: Resultsmentioning

confidence: 99%

Magnetic Slow Relaxation in a Metal–Organic Framework Made of Chains of Ferromagnetically Coupled Single‐Molecule Magnets

Huang

Garcia

Badiane

et al. 2018

Chemistry A European J

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We report the study of a Dy-based metal-organic framework (MOF) with unprecedented magnetic properties. The compound is made of nine-coordinated Dy magnetic building blocks (MBBs) with poor intrinsic single-molecule magnet behavior. However, the MOF architecture constrains the MBBs in a one-dimensional structure that induces a ferromagnetic coupling between them. Overall, the material shows a magnetic slow relaxation in absence of external static field and a hysteretic behavior at 0.5 K. Low-temperature magnetic studies, diamagnetic doping, and ab initio calculations highlight the crucial role played by the Dy-Dy ferromagnetic interaction. Overall, we report an original magnetic object at the frontier between single-chain magnets and single-molecule magnets that host intrachain couplings that cancel quantum tunneling between the MBBs. This compound is evidence that a bottom-up approach through MOF design can induce spontaneous organization of MBBs able to produce remarkable molecular magnetic materials.

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Section: Resultsmentioning

confidence: 99%

Magnetic Slow Relaxation in a Metal–Organic Framework Made of Chains of Ferromagnetically Coupled Single‐Molecule Magnets

Huang

Garcia

Badiane

et al. 2018

Chemistry A European J

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“…(1) was fitted to experimental data for a supramolecular aggregate containing SMMs, finding that it successfully explained the observed complex magnetic susceptibility and relaxation times behaviors. 42 Accurate spectral information on the magnetic excitation of the clusters can be extracted using various techniques, including inelastic neutron scattering, optical spectroscopic methods, magnetic susceptibility measurements and electron paramagnetic resonance (EPR). 44 Due to the energy scales involved in the problem, few of these techniques could provide meaningful magnetic information.…”

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confidence: 99%

Complex magnetic orders in small cobalt–benzene molecules

González

Alonso-Lanza

Delgado

et al. 2017

Phys. Chem. Chem. Phys.

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Organometallic clusters based on transition metal atoms are interesting because possible applications in spintronics and quantum information. In addition to the enhanced magnetism at the nanoscale, the organic ligands may provide a natural shield again unwanted magnetic interactions with the matrices required for applications. Here we show that the organic ligands may lead to non-collinear magnetic order as well as the expected quenching of the magnetic moments. We use different density functional theory (DFT) methods to study the experimentally relevant three cobalt atoms surrounded by benzene rings (Co3Bz3). We found that the benzene rings induce a ground state with non-collinear magnetization, with the magnetic moments localized on the cobalt centers and lying on the plane formed by the three cobalt atoms. We further analyze the magnetism of such a cluster using an anisotropic Heisenberg model where the involved parameters are obtained by a comparison with the DFT results. These results may also explain the recent observation of null magnetic moment of Co3Bz + 3 . Moreover, we propose an additional experimental verification based on electron paramagnetic resonance.

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“…A good strategy is the use of building-block approaches to link SMMs together employing carefully chosen linker groups that will provide weak inter-SMM interactions and ensure that discrete oligomeric species (and not polymers) are obtained. The groups of Papaefstathiou, Brechin, Christou, and Escuer, among others, have successfully contributed into this general synthetic goal (Stoumpos et al, 2009 ; Inglis et al, 2010 ; Cordero et al, 2011 ; Nguyen et al, 2011 , 2015 , 2016 ; Mowson et al, 2013 ). We herein present examples of the supramolecular approaches which have been almost exclusively developed in Mn SMM chemistry.…”

Section: The Years Of Design: Strict and Less Strict Synthetic Stratementioning

confidence: 99%

Coordination Clusters of 3d-Metals That Behave as Single-Molecule Magnets (SMMs): Synthetic Routes and Strategies

2018

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The area of 3d-metal coordination clusters that behave as Single-Molecule Magnets (SMMs) is now quite mature within the interdisciplinary field of Molecular Magnetism. This area has created a renaissance in Inorganic Chemistry. From the synthetic Inorganic Chemistry viewpoint, the early years of “try and see” exercises (1993–2000) have been followed by the development of strategies and strict approaches. Our review will first summarize the early synthetic efforts and routes for the preparation of polynuclear 3d-metal SMMs, and it will be then concentrated on the description of the existing strategies. The former involve the combination of appropriate 3d-metal-containing starting materials (simple salts with inorganic anions, metal cardoxylates, and pre-formed carboxylate clusters, metal phosphonates) and one or two primary organic ligands; the importance of the end-on azido group as a ferromagnetic coupler in 3d-metal SMM chemistry will be discussed. The utility of comproportionation reactions and the reductive aggregation route for the construction of manganese SMMs will also be described. Most of the existing strategies for the synthesis of SMMs concern manganese. These involve substitution of carboxylate ligands in pre-formed SMMs by other carboxylate or non-carboxylate groups, reduction procedures for the {Mn8IIIMn4IV} SMMs, spin “tweaking,” “switching on” SMM properties upon conversion of low-spin clusters into high-spin ones, ground-state spin switching and enhancing SMM properties via targeted structural distortions, the use of radical bridging ligands and supramolecular approaches. A very useful strategy is also the “switching on” of SMM behavior through replacement of bridging hydroxide groups by end-on azido or isocyanato ligands in clusters. Selected examples will be mentioned and critically discussed. Particular emphasis will be given on the criteria for the choice of ligands.

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Supramolecular aggregates of single-molecule magnets: exchange-biased quantum tunneling of magnetization in a rectangular [Mn₃]₄ tetramer

Abstract: Exchange-biased QTM within a magnetically-supramolecular tetramer of Mn3 single-molecule magnets with spin S = 6 has been analyzed.

Cited by 49 publications

References 105 publications

Magnetic Slow Relaxation in a Metal–Organic Framework Made of Chains of Ferromagnetically Coupled Single‐Molecule Magnets

Magnetic Slow Relaxation in a Metal–Organic Framework Made of Chains of Ferromagnetically Coupled Single‐Molecule Magnets

Complex magnetic orders in small cobalt–benzene molecules

Coordination Clusters of 3d-Metals That Behave as Single-Molecule Magnets (SMMs): Synthetic Routes and Strategies

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Supramolecular aggregates of single-molecule magnets: exchange-biased quantum tunneling of magnetization in a rectangular [Mn3]4 tetramer

Abstract: Exchange-biased QTM within a magnetically-supramolecular tetramer of Mn3 single-molecule magnets with spin S = 6 has been analyzed.

Cited by 49 publications

References 105 publications

Magnetic Slow Relaxation in a Metal–Organic Framework Made of Chains of Ferromagnetically Coupled Single‐Molecule Magnets

Magnetic Slow Relaxation in a Metal–Organic Framework Made of Chains of Ferromagnetically Coupled Single‐Molecule Magnets

Complex magnetic orders in small cobalt–benzene molecules

Coordination Clusters of 3d-Metals That Behave as Single-Molecule Magnets (SMMs): Synthetic Routes and Strategies

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Supramolecular aggregates of single-molecule magnets: exchange-biased quantum tunneling of magnetization in a rectangular [Mn₃]₄ tetramer