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

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

  • Marriott KER WestCHEM , School of Chemistry , University of Glasgow , Glasgow , G12 8QQ , UK . Email: mark.murrie@glasgow.ac.uk.
  • Bhaskaran L Department of Physics and NHMFL , Florida State University , Tallahassee , FL 32310 , USA . Email: shill@magnet.fsu.edu.
  • Wilson C WestCHEM , School of Chemistry , University of Glasgow , Glasgow , G12 8QQ , UK . Email: mark.murrie@glasgow.ac.uk.
  • Medarde M Laboratory for Developments and Methods , Paul Scherrer Institute , CH-5232 Villigen PSI , Switzerland.
  • Ochsenbein ST Laboratory for Neutron Scattering and Imaging , Paul Scherrer Institute , CH-5232 Villigen PSI , Switzerland.
  • Hill S Department of Physics and NHMFL , Florida State University , Tallahassee , FL 32310 , USA . Email: shill@magnet.fsu.edu.
  • Murrie M WestCHEM , School of Chemistry , University of Glasgow , Glasgow , G12 8QQ , UK . Email: mark.murrie@glasgow.ac.uk.
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  • 2017-08-01
Published in:
  • Chemical science. - 2015
English 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.
Language
  • English
Open access status
gold
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Persistent URL
https://sonar.ch/global/documents/269164
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