title: Supramolecular and redox chemistry of tetrathiafulvalene monocarboxylic acid with hydrogen-bonded pyridine and bipyridine molecules.
abstract: Although tetrathiafulvalene derivatives (TTFs) have been used as the redox-active unit in a lot of ion responsive receptors, only a few such examples of TTF carboxylic acids have been reported, especially about the responses to neutral organic molecules. In this work, electrochemical and spectral properties of dimethylthio-tetrathiafulvalene monocarboxylic acid (DMT-TTFCOOH) have been studied by both experimental methods and quantum chemical calculations. A square mechanism of proton transfer and electron transfer equilibriums was proposed. It is noteworthy that the process of oxidizing the TTF moiety of DMT-TTFCOOH could be controlled to obtain TTF(•+) radical cation or TTF(2+) dication by choosing suitable oxidizing reagents. Supramolecular responsive properties of DMT-TTFCOOH to py/bpy were investigated by cyclic voltammetry and (1)H NMR spectra. The results showed that the compound DMT-TTFCOOH is an electrochemically sensitive hydrogen bonding donor that can detect a tiny difference in the hydrogen bonding acceptor molecules. The theoretical calculations further confirm the results. The hydrogen-bonding structure of DMT-TTFCOOH-bpy in crystal was solved by X-ray diffraction analysis.
authors.affiliation: Department of Chemistry & Key Laboratory of Organic Synthesis of Jiangsu Province, Soochow University, Suzhou 215123, P. R. China. zhuqinyu@suda.edu.cn
authors.forename: Qin-Yu
authors.initials: QY
authors.lastname: Zhu
authors.forename: Qiong-Hua
authors.initials: QH
authors.lastname: Han
authors.forename: Ming-Yan
authors.initials: MY
authors.lastname: Shao
authors.forename: Jing
authors.initials: J
authors.lastname: Gu
authors.forename: Zheng
authors.initials: Z
authors.lastname: Shi
authors.forename: Jie
authors.initials: J
authors.lastname: Dai