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The first observed metal coordination of a 1,2,3-dithiazole: Towards the design of new molecular materials

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Title: The first observed metal coordination of a 1,2,3-dithiazole: Towards the design of new molecular materials
Author: Smithson, Chad Steven
Department: Department of Chemistry and Biochemistry
Advisor: Preuss, K.E.
Abstract: This thesis is an investigation of naphtho[1,2-'d '][1,2,3]dithiazolyl-4,5-dione and its use as a spin bearing ligand. The synthesis of the ligand in the 1+, 0 and 1- oxidation states is given, with the neutral ligand found to dimerize in the solid state. Cyclic voltammetry in MeCN reveals an Ecell of 0.80 V vs SCE, and chemical reversibility of the E1/2(1-/0) (-0.02 V) and E1/2 (0/1+) (0.78 V) couples. Despite numerous efforts, the open shell 2- oxidation state could not be stabilized. The first coordination species of a 1,2,3-DTA complex are provided with coordination of this ligand to Sb 5+, Ga3+ and Fe3+. Coordination occurs through the quinone oxygen atoms with the ligand always in the closed shell 1- oxidation state as determined from bond lengths. The crystal packing is observed to be largely governed by electrostatics, forming long chains through close SC???l and SO??? interactions.
URI: https://hdl.handle.net/10214/26104
Date: 2011
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