Issue 12, 2015

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


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)

Supplementary files

Article information

Article type
Edge Article
03 Aug 2015
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
Creative Commons BY license

Chem. Sci., 2015,6, 6823-6828

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

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity