Department of Chemistry & Key Laboratory of Organic Synthesis of Jiangsu Province, Soochow University, Suzhou 215123, P. R. China.
J Phys Chem B. 2012 Apr 12;116(14):4239-47. doi: 10.1021/jp2124179. Epub 2012 Mar 30.
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.
尽管四硫富瓦烯衍生物（TTFs）已被用作许多离子响应受体中的氧化还原活性单元，但只有少数 TTF 羧酸的此类实例被报道，特别是关于对中性有机分子的响应。在这项工作中，通过实验方法和量子化学计算研究了二甲基硫代四硫富瓦烯单羧酸（DMT-TTFCOOH）的电化学和光谱性质。提出了质子转移和电子转移平衡的四方机制。值得注意的是，通过选择合适的氧化剂，可以控制 DMT-TTFCOOH 的 TTF 部分的氧化过程，以获得 TTF(•+)自由基阳离子或 TTF(2+)二阳离子。通过循环伏安法和（1）H NMR 光谱研究了 DMT-TTFCOOH 对 py/bpy 的超分子响应性质。结果表明，该化合物 DMT-TTFCOOH 是一种电化学敏感的氢键供体，可以检测到氢键受体分子的微小差异。理论计算进一步证实了这一结果。通过 X 射线衍射分析解决了 DMT-TTFCOOH-bpy 在晶体中的氢键结构。
