Journal
CHEMICAL SCIENCE
Volume 6, Issue 12, Pages 6823-6828Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5sc02854j
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Funding
- UK Engineering and Physical Sciences Research Council [EP/J018147/1]
- European Community [290605]
- NSF [DMR-1309463, DMR-1157490]
- State of Florida
- EPSRC [EP/J018147/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/J018147/1] Funding Source: researchfish
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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)(2)Cl-3]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.
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