高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (2): 193-199.doi: 10.7503/cjcu20160625

• 有机化学 • 上一篇    下一篇

含吡啶基四硫富瓦烯衍生物的合成、 结构和电化学性质

赵邦屯1(), 马书修2, 陶晶晶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:2016-09-05 出版日期:2017-02-10 发布日期:2016-12-28
  • 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研究. E-mail: zhuwm@zzu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 201172105)资助

Synthesis, Structures and Electrochemical Properties of Pyridine-based Tetrathiafulvalene Derivatives

ZHAO Bangtun1,*(), MA Shuxiu2, TAO Jingjing2, 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:2016-09-05 Online:2017-02-10 Published:2016-12-28
  • 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:

在乙酰乙酸乙酯和氧化亚铜共同催化下, 二-(1,3-二硫环戊烯-2-硫酮-4,5-二硫)合锌酸四乙基铵盐分别与2-碘吡啶(1a)、 3-碘吡啶(1b)和4-碘吡啶(1c)反应, 制得硫酮化合物2,3-二(2-吡啶硫基)-1,3-二硫环戊烯-2-硫酮(2a)、 2,3-二(3-吡啶硫基)-1,3-二硫环戊烯-2-硫酮(2b)和2,3-二(4-吡啶硫基)-1,3-二硫环戊烯-2-硫酮(2c). 在醋酸汞催化下, 硫酮化合物2a, 2b和2c分别被氧化为2,3-二(2-吡啶硫基)-1,3-二硫环戊烯-2-酮(3a)、 2,3-二(3-吡啶硫基)-1,3-二硫环戊烯-2-酮(3b)和2,3-二(4-吡啶硫基)-1,3-二硫环戊烯-2-酮(3c). 以亚磷酸三乙酯为偶联剂, 氧酮化合物3a, 3b和3c分别发生自偶联反应生成2,3,6,7-四(2-吡啶硫基)四硫富瓦烯(4a)、 2,3,6,7-四(3-吡啶硫基)四硫富瓦烯(4b)和2,3,6,7-四(4-吡啶硫基)四硫富瓦烯(4c). 采用核磁共振波谱(NMR)、 傅里叶变换红外光谱(FTIR)和质谱(MS)分析了所合成化合物的结构和组成, 通过X射线衍射分析确认了吡啶基四硫富瓦烯衍生物4b和4c的晶体结构. 循环伏安法研究结果表明, 化合物4a, 4b和4c呈现准可逆的两电子转移过程, 结合量子化学计算, 分析了不同位置取代的吡啶基对四硫富瓦烯电化学电势的影响.

关键词: 四硫富瓦烯, 吡啶, 晶体结构, 循环伏安, 量化计算

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) zincate 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-tetrathiafulvalene 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 resonance spectroscopy(1H NMR and 13C NMR), fourier transform infrared spectroscopy(FTIR) and mass spectroscopy(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.

Key words: Tetrathiafulvalene, Pyridine, Crystal structure, Cyclic voltammetry, Quantum chemical calculation

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