有机化学 ›› 2017, Vol. 37 ›› Issue (2): 394-402.DOI: 10.6023/cjoc201606040 上一篇    下一篇

研究论文

1,4-双[2-(4-吡啶基)乙烯基]苯衍生物的合成、光谱性质及理论研究

欧亚平a, 张静b, 庾江喜a, 朱小明a   

  1. a 衡阳师范学院化学与材料科学学院 功能金属有机材料湖南省普通高等学校重点建设实验室 衡阳 421008;
    b 华中师范大学化学学院 农药与化学生物学教育部重点实验室 武汉 430079
  • 收稿日期:2016-06-29 修回日期:2016-09-02 出版日期:2017-02-25 发布日期:2016-10-18
  • 通讯作者: 欧亚平 E-mail:ouyaping@hynu.edu.cn
  • 基金资助:

    湖南省高校重点实验室开放基金(No.GN15K05)及衡阳师范学院科研启动基金(No.14B23)资助项目.

Synthesis, Spectral Properties and Theoretical Studies of 1,4-Bis[2-(4-pyridyl)ethenyl]benzene Derivatives

Ou Yapinga, Zhang Jingb, Yu Jiangxia, Zhu Xiaominga   

  1. a Key Laboratory of Functional Organometallic Materials of Hunan Province College, College of Chemistry and Material Science, Hengyang Normal University;Hengyang 421008;
    b Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, Central China Normal University, Wuhan 430079
  • Received:2016-06-29 Revised:2016-09-02 Online:2017-02-25 Published:2016-10-18
  • Supported by:

    Project supported by the Opening Subjects of Key Laboratory of Functional Organometallic Materials of Hunan Province (No. GN15K05), and the Scientific Research Foundation of the Hengyang Normal University (No. 14B23).

通过经典的Witting-Horner反应及Sonogashira交叉偶联反应以较高的产率合成得到4个不对称型氢键受体分子1,4-双[2-(4-吡啶基)乙烯基]苯衍生物,并对其结构及光谱性质开展了研究.系列化合物均通过核磁、元素分析及质谱的表征,晶体结构表明由于苯环邻位芳环乙炔基的空间效应导致氢键组装的构型发生改变.紫外可见光谱结合含时密度泛函理论(TDDFT)计算表明目标化合物在紫外区域均呈现出强烈的π→π*及ICT跃迁吸收.荧光光谱表明随着共轭体系的逐渐增大也导致了它们的发射峰有一个红移的倾向,且有利于分子之间形成π-π堆积.以上结果将为后续的氢键自组装的区域选择性及光照环化实验研究提供了一定的合成基础及理论依据.

关键词: 不对称氢键受体分子, 1,4-双[2-(4-吡啶基)乙烯基]苯, 晶体结构, 光谱性质

Four asymmetric hydrogen-bond acceptors of 1,4-bis[2-(4-pyridyl)ethenyl]benzene derivatives with higher yields were synthesized through the classical Witting-Horner and Sonogashira cross-coupling reactions, and their structures and spectral properties were investigated. The series of compounds all have been characterized by NMR, MS and element analysis. Crystal structures indicated that the conformation of hydrogen-bond self-assemble may be change due to the hindrance effect from the arylacetyl group in o-position of benzene. UV-Vis spectra combined with time-dependent density functional theory (TDDFT) calculation results showed that target compounds all display a strong π→π* and ICT transition absorptions. Fluorescence spectrum indicated that gradual increasing of conjugate systems make their emission peak tend to a red shift, which is conducive to π-π accumulation. Above results will provide certain synthetic basis and theoretical foundation for subsequent studies about regioselectivity of hydrogen-bond self-assemble and cyclization reactions from light.

Key words: Asymmetric hydrogen-bond acceptor, 1,4-Bis[2-(4-pyridyl)ethenyl]benzene, Crystal structure, Spectral properties