1 research outputs found
Studies of DTF and TTFV-based donor-acceptor systems and redox-active polymer thin films
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