高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (7): 1449-1454.doi: 10.7503/cjcu20180145

• 有机化学 • 上一篇    下一篇

含噻吩和吡啶基的插烯式四硫富瓦烯衍生物的合成、 结构和电化学性质

赵邦屯1(), 陶晶晶2, 陈小纪2, 付慧敏2, 朱卫民2()   

  1. 1. 洛阳师范学院化学化工学院, 洛阳 471022
    2. 郑州大学化学与分子工程学院, 郑州 450010
  • 收稿日期:2018-02-28 出版日期:2018-07-10 发布日期:2018-06-13
  • 作者简介:联系人简介: 赵邦屯, 男, 博士, 教授, 主要从事超分子化学方面的研究. E-mail:zbt@lynu.edu.cn; 朱卫民, 男, 博士, 副教授, 主要从事功能有机合成方面的研究. E-mail:zhuwm@zzu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 21172105)资助.

Synthesis, Structure and Electrochemistry of Tetrathiafulvalene Vinylogues Bearing Thienyl and Pyridyl Groups

ZHAO Bangtun1,*(), TAO Jingjing2, CHEN Xiaoji2, FU Huimin2, ZHU Weimin2,*()   

  1. 1. College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, China
    2. College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450010, China
  • Received:2018-02-28 Online:2018-07-10 Published:2018-06-13
  • Contact: ZHAO Bangtun,ZHU Weimin E-mail:zbt@lynu.edu.cn;zhuwm@zzu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.21172105).

摘要:

在亚磷酸三乙酯催化作用下, 2,3-二(2-吡啶硫基)-1,3-二硫环戊烯-2-硫酮(1)分别与2-噻吩甲醛(2a)和3-噻吩甲醛(2b)发生成烯偶联反应, 生成二硫富瓦烯化合物[2-(2-噻吩)亚基-1,3-二硫环戊烯-4,5-二硫基]双邻吡啶(3a)和[2-(3-噻吩)亚基-1,3-二硫环戊烯-4,5-二硫基]双邻吡啶(3b); 含噻吩和吡啶基的二硫富瓦烯化合物3a和3b分别经过单质碘诱导氧化偶联反应和硫代亚硫酸钠还原反应, 得到含噻吩和吡啶基的插烯式四硫富瓦烯化合物1,2-双(4,5-二邻吡啶硫代-1,3-二硫环戊烯-2-亚基)-1,2-双(2-噻吩基)乙烷(4a)和1,2-双(4,5-二邻吡啶硫代-1,3-二硫环戊烯-2-亚基)-1,2-双(3-噻吩基)乙烷(4b). 利用核磁共振波谱(NMR)、 傅里叶变换红外光谱(FTIR)和质谱(MS)方法对插烯式四硫富瓦烯衍生物(4a和4b)分别进行了表征, 同时采用X射线单晶衍射法分析确证了化合物3a, 3b, 4a和4b的晶体结构. 循环伏安法研究结果表明, 化合物4a和4b呈现准可逆的两电子转移行为. 结合量子化学理论计算, 探讨了噻吩基的位置差异对化合物4a和4b电化学电位的影响.

关键词: 插烯式四硫富瓦烯, 噻吩, 吡啶, 循环伏安, 量子化学计算

Abstract:

Through triethylphosphite-mediated cross-coupling reaction, 4,5-bis(pyridin-2-ylthio)-1,3-dithiole-2-thione(1) reacted with 2-thiophenecarboxaldehyde(2a) or 3-thiophenecarboxaldehyde(2b) to give 2,2'-[(2-(thiophen-2-ylmethylene)-1,3-dithiole-4,5-diyl)bis(sulfanediyl)]dipyridine(3a) and 2,2'-[(2-(thiophen-3-ylmethylene)-1,3-dithiole-4,5-diyl)bis(sulfanediyl)]dipyridine(3b) with the yields of 64% and 59%, respectively. The dithiafulvalene compounds possessing thienyl and pyridyl groups 3a and 3b were subjected to an iodine-induced oxidative dimerization reactions and then a brief reductive aqueous workup with Na2S2O3 to gain tetrathiafulvalene vinylogues 1,2-bis(4,5-bis(pyridin-2-ylthio)-1,3-dithiol-2-ylidene)-1,2-di(thiophen-2-yl)ethane(4a) and 1,2-bis(4,5-bis(pyridin-2-ylthio)-1,3-dithiol-2-ylidene)-1,2-di(thiophen-3-yl)ethane(4b) with the yields of 24% and 22%, respectively. All novel compounds were identified by the nuclear magnetic resonance spectroscopy(NMR), fourier transform infrared spectroscopy(FTIR) and mass spectroscopy(MS) methods. Meanwhile, the structures of compounds 3a, 3b, 4a and 4b were characterized by X-ray diffraction analysis. The cyclic voltammograms showed that the tetrathiafulvalene vinylogues 4a and 4b displayed quasi-reversible one two-electron redox processes. Combined with quantum chemical calculations, effects of the different thienyl and pyridyl groups substituted tetrathiafulvalene vinylogues 4a and 4b on electrochemical potentials were analysised.

Key words: Tetrathiafulvalene vinylogue, Thiophene, Pyridine, Cyclic voltammetry, Quantum chemical calculation