Synthesis of carboxylated dithiafulvenes and tetrathiafulvalene vinylogues as redox-active ligands

Adows, Hadeel (2016) Synthesis of carboxylated dithiafulvenes and tetrathiafulvalene vinylogues as redox-active ligands. Masters thesis, Memorial University of Newfoundland.

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Abstract

The excellent electron-donating properties of dithiafulvene (DTF) derivatives and tetrathiafulvene vinylogues (TTFVs) make them versatile building components in the synthesis of functional organic optoelectronic materials and devices. The recent synthesis and characterization studies on functionalized DTF and TTFV derivatives have disclosed promising applicability in the development of advanced optoelectronic, photonic, and redox-active nanomaterials. To cast more light in this aspect, the central theme of this MSc thesis is based upon the design and synthesis of a new class of DTF and TTFV derivatives containing carboxylate esters and carboxylic groups as active ligands for metal coordination. The detailed research is diversified into two projects. In the first project, the ability of these carboxylated DTFs and TTFVs to reduce Au(III) species in organic media was investigated by various spectroscopic and microscopic analyses (e.g., UV-Vis-NIR, cyclic voltammetry, SEM, and DLS). It was found that a carboxylic DTF was able to directly reduce Au(III) to Au(0) in dipolar aprotic solvents (DMF, DMSO), and the resulting Au(0) could be further stabilized by the carboxylic DTF as nanoparticles with sizes of tens of nanometers. The finding point to a useful approach for the preparation of functionalized gold nanoparticles with redox-activity. In the second project, the carboxylic TTFV derivative was investigated as a ligand for complexation with a number of metal cations, with the attempt to form redox-active coordination polymers or metal-organic frameworks (MOFs). The detailed reactivity and properties were characterized by IR, single-crystal and power X-ray differaction analyses.

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