Coordination Complexes of 1,2,3-Dithiazolyl-o-naphthoquinone Ligands with Potential Conductive and Magnetic Applications

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Dinsdale, Danielle
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University of Guelph

This thesis presents coordination complexes of 1,2,3-dithiazole (DTA) molecules, 4-hydroxy-naphtho[1,2-d][1,2,3]dithiazol-5-one (o-DTANQOH) and 4-methoxy-naphtho[1,2-d][1,2,3]dithiazol-5-one (o-DTANQOMe), for the development of magnetic and conductive materials. A series of boron coordination complexes have been synthesized, [B(o-DTANQ)2][X] (X=Cl, FeCl4, OTf, GaCl4). Cyclic voltammetry of [B(o-DTANQ)2][X] (X=OTf, GaCl4) in CH3CN reveals an Ecell of 0.16 V vs. SCE with reversible +1/0 and 0/-1 redox couples. Reduction to the neutral radical state has been attempted but definitive proof has not been obtained. A new 1,2,3-DTA molecule, o-DTANQOMe, has been synthesized. Electrochemical measurements reveal a chemically reversible reduction to the radical anion state and the macromolecule cyanostar can increase the lifetime of this oxidation state, tested using cyclic voltammetry. Reactions of o-DTANQOMe with Ce(hfac)3, Cr(hfac)2, SbCl3, and SbI3 are presented and discussed. A series of complexes M(o-DTANQ)x (where M=Fe, Mn, Co and x=2, 3) and Ln(o-DTANQ)3·XH2O (where Ln=La, Gd, Ce and X=2, 3), where the ligand is in the closed-shell oxidation state have been synthesized.

thiazyl, dithiazolyl, conductivity, radical, coordination complex, naphthoquinone, lanthanide, boron, transition metal