386 research outputs found

    Influence of antisymmetric exchange interaction on quantum tunneling of magnetization in a dimeric molecular magnet Mn6

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    We present magnetization measurements on the single molecule magnet Mn6, revealing various tunnel transitions inconsistent with a giant-spin description. We propose a dimeric model of the molecule with two coupled spins S=6, which involves crystal-field anisotropy, symmetric Heisenberg exchange interaction, and antisymmetric Dzyaloshinskii-Moriya exchange interaction. We show that this simplified model of the molecule explains the experimentally observed tunnel transitions and that the antisymmetric exchange interaction between the spins gives rise to tunneling processes between spin states belonging to different spin multiplets.Comment: 5 pages, 4 figure

    Tunable dipolar magnetism in high-spin molecular clusters

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    We report on the Fe17 high-spin molecular cluster and show that this system is an exemplification of nanostructured dipolar magnetism. Each Fe17 molecule, with spin S=35/2 and axial anisotropy as small as D=-0.02K, is the magnetic unit that can be chemically arranged in different packing crystals whilst preserving both spin ground-state and anisotropy. For every configuration, molecular spins are correlated only by dipolar interactions. The ensuing interplay between dipolar energy and anisotropy gives rise to macroscopic behaviors ranging from superparamagnetism to long-range magnetic order at temperatures below 1K.Comment: Replaced with version accepted for publication in Physical Review Letter

    High nuclearity Ni(ii) cages from hydroxamate ligands

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    The synthesis, structural and magnetic characterisation of a family of Ni(ii) cages built from hydroxamate ligands is presented. Two pentanuclear 12-MCNi(ii)-4 metallacrowns [Ni5(L1) 4(MeOH)4](ClO4)2·2MeOH (1) and [Ni5(L1)4(py)5](ClO 4)2·H2O (2) (where L1H 2 = 2-(dimethylamino)phenylhydroxamic acid) share analogous, near-planar {Ni5(L1)4}2+ cores, but differ in the number and nature of the ligands located at the axial Ni(ii) sites; the addition of pyridine converting square planar Ni(ii) ions to square-based pyramidal and octahedral Ni(ii) ions, introducing extra paramagnetic metal centres which 'switch on' additional magnetic superexchange pathways. Subtle variations in the reaction scheme used to produce complexes 1 and 2 result in both a change of topology and an increase in nuclearity, through isolation of the hepta- and nonametallic complexes [Ni7(L 1H)8(L1)2(H2O) 6](SO4)·15H2O (3), [Ni 9(μ-H2O)2(L2)6(L 2H)4(H2O)2](SO4) ·29H2O (4) and [Ni9(μ-H2O) 2(L2)6(L2H)4(H 2O)2](ClO4)2·2MeOH· 18H2O (5) (where L2H2 = 2-(amino) phenylhydroxamic acid). Complementary dc magnetic susceptibility studies and DFT analysis indicate dominant antiferromagnetic exchange interactions in 1, 2, 4 and 5, but competing ferro- and antiferromagnetic exchange in 3. © the Partner Organisations 2014.EKB would like to thank the EPSRC for funding (SS). GR acknowledges financial support from the Government of India through the Department of Science and Technology (SR/S1/IC-41/2010; SR/NM/NS-1119/2011) and generous computational resources from the Indian Institute of Technology-Bombay. MKS thanks the University Grants Commission for a Junior Research Fellowship.Published versio

    Increasing the dimensionality of cryogenic molecular coolers: Gd-based polymers and metal-organic frameworks

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    Trabajo presentado a la 5th International Conference on Molecular Materials (MolMat) celebrada en Barcelona (España) del 3 al 6 de julio de 2012.The magnetothermal properties of a coordination polymer and a metal-organic framework (MOF) based on Gd 3+ ions are reported. An equally large cryogenic magnetocaloric effect (MCE) is found, irrespective of the dimensionality. This combined with their robustness makes them appealing for widespread magnetic refrigeration applications. © 2012 The Royal Society of Chemistry.We are grateful to MINECO (contracts MAT2009-13977-C03, MAT2011-24284 and CSD2007-00010), EC (for a Marie Curie-IEF to GL), University of Granada (for a postdoctoral fellowship to MAP), and EPRSC for funding.Peer Reviewe

    Phthalocyanine-polyoxotungstate lanthanide double deckers

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    Acetate ligand metathesis results in the first hybrid [MIII(Pc)(PW11O39)]6− (M = Y, Dy, Tb) double-decker scaffolds, where a phthalocyanate (Pc2−) and one of the conceptually most simple polyoxotungstates, a monolacunary Keggin cluster, are interlinked via a single rare earth ion. Characterisation includes high-resolution mass spectrometry, synchrotron-based single-crystal X-ray diffraction, various spectroscopic and electrochemical methods, and magnetic studies revealing slow relaxation of the magnetisation for the Dy derivate
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