高等学校化学学报2017，Vol.38Issue(2)：193-199,7.DOI:10.7503/cjcu20160625
含吡啶基四硫富瓦烯衍生物的合成、结构和电化学性质
Synthesis, Structures and Electrochemical Properties of Pyridine-based Tetrathiafulvalene Derivatives?
摘要
Abstract
Using the ethyl acetoacetate/Cu2O system, 4,5-bis(pyridin-2-ylthio)-1,3-dithiole-2-thione(2a), 4,5-bis ( pyridin-3-ylthio )-1, 3-dithiole-2-thione ( 2b ) and 4, 5-bis ( pyridin-4-ylthio )-1, 3-dithiole-2-thione (2c) were prepared by the reaction of di(tetraehylammonium)-bis(1,3-dithiol-2-thione-4,5-dithiocate) zinc-ate with 2-iodopyridine(1a), 3-iodopyridine(1b) and 4-iodopyridine(1c) with the yields of 88%, 55% and 60%, respectively. Thiones 2a, 2b and 2c were conversed to 4,5-bis(pyridin-2-ylthio)-1,3-dithiole-2-one (3a), 4,5-bis(pyridin-3-ylthio)-1,3-dithiole-2-one(3b) and 4,5-bis(pyridin-4-ylthio)-1,3-dithiole-2-one (3c) under the presence of Hg(OAc)2 in almost quantitative yields. Consequently, the pyridine-tetrathiaful-valene compounds 2,3,6,7-tetrakis(pyridine-2-ylthio) tetrathiafulvalene(4a), 2,3,6,7-tetrakis(pyridine-3-ylthio) tetrathiafulvalene(4b) and 2,3,6,7-tetrakis(pyridine-4-ylthio) tetrathiafulvalene(4c) were obtained correspondingly through triethylphosphite-mediated self-coupling reactions of 3a, 3b and 3c with the yields of 80%, 74% and 69%. All novel compounds were characterized by proton and carbon nuclear magnetic reso-nance spectroscopy(1H NMR and 13C NMR), fourier transform infrared spectroscopy(FTIR) and mass spec-troscopy( MS) methods. Meanwhile, the structures of 4b and 4c was identified by X-ray diffraction analysis. The cyclic voltammograms showed that the pyridine-tetrathiafulvalene 4a, 4b and 4c displayed two-electron quasi-reversible redox processes. Combined with quantum chemical calculations, the effects of the different pyridyl substituted tetrathiafulvalenes 4a, 4b and 4c on electrochemical potentials were analysised.关键词
四硫富瓦烯/吡啶/晶体结构/循环伏安/量化计算Key words
Tetrathiafulvalene/Pyridine/Crystal structure/Cyclic voltammetry/Quantum chemical calcula-tion分类
化学化工引用本文复制引用
赵邦屯,马书修,陶晶晶,朱卫民..含吡啶基四硫富瓦烯衍生物的合成、结构和电化学性质[J].高等学校化学学报,2017,38(2):193-199,7.基金项目
国家自然科学基金(批准号:201172105)资助.? Supported by the National Natural Science Foundation of China( No. 21172105) . （批准号:201172105）
