Acetylenic tetrathiafulvalenes and related macrocyclic systems

Chen, Guang (2011) Acetylenic tetrathiafulvalenes and related macrocyclic systems. Doctoral (PhD) thesis, Memorial University of Newfoundland.

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Abstract

This thesis reports the study of a series of novel acetylenic π-extended tetrathiafulvalene derivatives (exTTFs). The detailed research is divided into two major projects. In the first project, acetylenic anthraquinoid-type exTTFs (referred to as TTFAQs) were synthesized and characterized. The target compounds have rigid macrocyclic enyne conjugated π-frameworks which can be constructed by a one-pot, 4-fold Sonogashira coupling strategy. The molecules show interesting solid-state stacking in single crystals, and rich electronic and redox properties as characterized by UV-vis and fluorescence spectroscopy, cyclic voltammetry, and spectroelectrochemistry. In the second project, a series of acetylenic tetrathiafulvalene vinylogues (TTFVs) and their structural analogues, oligoyne-derived TTFs, were synthesized and studied. Two routes are explored for the selective formation of macrocyclic TTFV and acyclic TTFV oligomers. Electronic and redox properties of these molecules were characterized by various instrumental analyses. Oligoyne-TTFs undergo electropolymerization to form stable TTFV-containing polymer films which show electrochromic behavior. Solid-state reactivity of oligoyne-TTFs were studied by differential scanning calorimetric and thermogravimetric analysis. Finally, in a side project, a series of TTFV-centered tweezer-like molecules and TTFV-crown ether hybrids were designed and synthesized as supramolecular hosts for [60]fullerene and metal cations.

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