A collection of studies are reported that focus on the examination of exchange interactions in complexes containing paramagnetic ions with a large magnetic anisotropy. A number of complementary techniques are used to analyse the complicated systems that arise, including high-field high-frequency electron paramagnetic resonance, inelastic neutron scattering, SQUID magnetometry, and ab initio calculations. The nuclearity of the complexes ranges from dimetallic, to trimetallic, to octametallic. A family of five water- and carboxylate-bridged nickel(II) dimetallics are the focus of a magneto-structural correlation study that succeeds in measuring the magnitude of the exchange interaction despite dominating effects from large zero-field splitting effects. Similar work is reported for four cobalt(II) analogues of these compounds, with the relationship between exchange interactions and geometry also being probed by pressure INS. Charge density studies that combine high resolution X-ray and neutron diffraction studies are reported on cobalt and nickel analogues from the same family of dimetallics, revealing strong evidence for non-direct exchange. A family of four trimetallic triangle complexes containing two nickel(II) ions and one chromium(III) ion bridged by a central fluoride and a total of six carboxylates are reported, and the exchange interactions are elucidated from a global model that accounts for the low-field magnetic, heat capacity, and EPR data. Two new octametallic vanadium(III) wheels—where each pair of adjacent metals are bridged by a fluoride and two carboxylates—are reported along with preliminary results from magnetic measurements and solid state proton NMR spectra, which reveal significant field-dependent effects arising from level crossings at high fields.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:632255 |
| Date | January 2014 |
| Creators | Walsh, James Paul Slater |
| Publisher | University of Manchester |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | https://www.research.manchester.ac.uk/portal/en/theses/anisotropy-in-molecular-magnetism(11474b91-0d3d-4b0a-97cd-214d1713674e).html |
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