This thesis provides the first example of coordination of a 1,2,3-dithiazolyl (1,2,3-DTA) ligand through a N, O bidentate pocket that is reproducible in high purity and bulk quantities. More importantly, it reports the first magnetometry measurements on metal complexes of a 1,2,3-DTA ligand.
The radical ligand 1,2,3-dithiazolyl-6,7-dimethyl-1,4-naphthoquinone (6,7-Me2DTANQ) has been prepared and fully characterized. Coordination complexes of 6,7-Me2DTANQ have also been prepared and the resulting species’ structural and magnetic properties are presented. The transition metal ions Ni2+ and Mn2+ produce volatile trinuclear M(hfac)2-Rad-M(hfac)2-Rad-M(hfac)2 complexes. The spin ground state of the trinuclear Mn complex ST = 13/2 results from antiferromagnetic (AFM) coupling. Short sulfur-sulfur contacts and sulfur-oxygen contacts between trinuclear complexes produce weak AFM coupling interactions between trimer units. The lanthanide ions Nd3+, Gd3+ and Dy3+ produce volatile [Ln(hfac)3-Rad]n complexes. The spin ground state of the Gd polymer is ST = 3 per monomeric unit due to Gd3+‒radical AFM coupling.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:OGU.10214/4320 |
| Date | 09 November 2012 |
| Creators | Sullivan, David |
| Contributors | Preuss, Kathryn |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Thesis |
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