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Issue 12, 2015
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Pushing the limits of magnetic anisotropy in trigonal bipyramidal Ni(II)

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Abstract

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 (1) 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. 1 displays field-induced slow magnetic relaxation, which is rare for monometallic Ni(II) complexes due to efficient spin–lattice and quantum tunnelling relaxation pathways.

Graphical abstract: Pushing the limits of magnetic anisotropy in trigonal bipyramidal Ni(ii)

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Publication details

The article was received on 03 Aug 2015, accepted on 07 Sep 2015 and first published on 08 Sep 2015


Article type: Edge Article
DOI: 10.1039/C5SC02854J
Citation: Chem. Sci., 2015,6, 6823-6828
  • Open access: Creative Commons BY license
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    Pushing the limits of magnetic anisotropy in trigonal bipyramidal Ni(II)

    K. E. R. Marriott, L. Bhaskaran, C. Wilson, M. Medarde, S. T. Ochsenbein, S. Hill and M. Murrie, Chem. Sci., 2015, 6, 6823
    DOI: 10.1039/C5SC02854J

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