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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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Article information


Submitted
03 Aug 2015
Accepted
07 Sep 2015
First published
08 Sep 2015

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2015,6, 6823-6828
Article type
Edge Article
Author version available

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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