Synthesis and Magnetic Properties of 1,2,3-Dithiazolyl Coordination Complexes

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.