Pushing the limits of magnetic anisotropy in trigonal bipyramidal Ni(II)

Marriott, K. E.R., Bhaskaran, L., Wilson, C. , Ochsenbein, S. T., Hill, S. and Murrie, M. (2015) Pushing the limits of magnetic anisotropy in trigonal bipyramidal Ni(II). Chemical Science, 6(12), pp. 6823-6828. (doi: 10.1039/C5SC02854J) (PMID:28757973) (PMCID:PMC5508675)

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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.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Murrie, Professor Mark and Wilson, Dr Claire and Marriott, Miss Katie
Authors: Marriott, K. E.R., Bhaskaran, L., Wilson, C., Ochsenbein, S. T., Hill, S., and Murrie, M.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemical Science
Publisher:Royal Society of Chemistry
ISSN:2041-6520
ISSN (Online):2041-6539
Published Online:08 September 2015
Copyright Holders:Copyright © 2015 Royal Society of Chemistry
First Published:First published in Chemical Science 6(12): 6823-6828
Publisher Policy:Reproduced under a Creative Commons License
Data DOI:10.5525/gla.researchdata.205

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
592671Mapping magnetic anistrophy: rational design of nanomagnets with increased blocking temperatures.Mark MurrieEngineering & Physical Sciences Research Council (EPSRC)EP/J018147/1CHEM - CHEMISTRY