Studies of DTF and TTFV-based donor-acceptor systems and redox-active polymer thin films

Afzali, Azadeh (2022) Studies of DTF and TTFV-based donor-acceptor systems and redox-active polymer thin films. Masters thesis, Memorial University of Newfoundland.

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Abstract

1,4-Dithiafulvene (DTF) is a five-member heterocycle that has been frequently used as a redox-active molecular building block in various organic electronic materials. The combination of two DTF groups via an exo-ring C=C bond leads to formation of well-known tetrathiafulvalene (TTF), which has been extensively studied since the first discovery of its metallic conductivity. Previous research has demonstrated that DTF and tetrathiafulvalene vinylogue (TTFV)-based conjugated molecules and polymers show favored intermolecular interactions (e.g., π–π stacking and chargetransfer interactions) with electron-deficient nitroaromatic compounds (NACs), owing to the electron-donating nature of DTF and TTFV groups. Such properties can be utilized in the design of chemical sensors for detection of NACs, which are an important class of pollutants in the environment. To further understand the interplay between NACs and DTF/TTFV-containing π-systems, a group donor–acceptor ensembles containing nitrophenyl-substituted DTF and TTFV moieties have been investigated in this thesis work. Detailed synthetic methods and structure-property relationships will be discussed in the first chapter. In particular, the structural, electronic, and electrochemical redox properties were systematically examined by Xray single crystallographic, UV-Vis absorption, and cyclic voltametric analyses, in conjunction with density functional theory (DFT) modeling. With the fundamental properties characterized and understood, a new type of TTFV-based redox-active polymer was next designed and prepared. In the second part of this project, a strategy of double-layer polymer film will be introduced. With this method, robust and redox-active TTFV polymer thin films could be efficiently generated on the surface of glassy carbon electrodes. These modified electrodes were found to show sensitive responses to various phenolic compounds at low concentrations (10−8 to 10−7M), suggesting promising application in rapid electrochemical sensing of phenol derivatives and related chemicals.

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