Chin. J. Org. Chem. ›› 2018, Vol. 38 ›› Issue (10): 2680-2692.DOI: 10.6023/cjoc201805004 Previous Articles     Next Articles



高洪磊a,b, 杨笑迪c, 辛涵申b, 高铁阵b, 龚和贵a, 高希珂b   

  1. a 上海大学理学院化学系 上海 200444;
    b 中国科学院上海有机化学研究所 中国科学院有机功能分子合成与组装化学重点实验室 上海 200032;
    c 上海中医药大学科学与技术实验中心 上海 201203
  • 收稿日期:2018-05-02 修回日期:2018-06-03 发布日期:2018-06-06
  • 通讯作者: 杨笑迪,;龚和贵,;高希珂,;;
  • 基金资助:


Design, Synthesis and Properties of 2/6-Aryl Substituted Azulene Derivatives

Gao Hongleia,b, Yang Xiaodic, Xin Hanshenb, Gao Tiezhenb, Gong Heguia, Gao Xikeb   

  1. a Department of Chemistry, College of Science, Shanghai University, Shanghai 200444;
    b Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032;
    c Experiment Center for Science and Technology, Shanghai University of Traditional Chinese Medicine, 1200 Cai Lun Road, Shanghai 201203
  • Received:2018-05-02 Revised:2018-06-03 Published:2018-06-06
  • Contact: 10.6023/cjoc201805004;;
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21522209) and the Strategic Priority Research Program (No. XDB12010100).

Six 2/6-aryl substituted azulene derivatives 16 were designed and synthesised. Compounds 13 and 46 are 2-and 6-substituted derivatives, respectively, where the arly substituents were pentafluorobenzene, benzene and α-thiophene. The UV-Vis spectra, fluorescence spectra, electrochemical properties and proton-responsive properties of 16 were studied. To investigate the molecular sturcture, absorption spectra and energy levels of compounds 16, density functional theory (DFT) calculations were carried out. In comparison with the UV-Vis spectra of azulene, the absorption of S0→S2 transition of 16 showed red-shift (Δλ=6~68 nm). Owing to the strong electron-donating ability of α-thiophene group, remarkable bathochromic shifts of 3 and 6λ=68 and 48 nm, respectively) were obseved. The fluorescence spectra revealed that 4 (?F=0.082) has the highest fluorescence quantum yield of 16, while 1-H+ (?F=0.359) has the highest fluorescence quantum yield of the protonated compounds 1-H+6-H+, benefiting from the electron-withdrawing pentafluorophenyl group of 1 and 1-H+. Moreover, the electrochemical analysis and DFT calculations demonstated that the introduction of electron-withdrawing pentafluorophenyl unit in the 2/6-positon of azulene can significantly lower the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). In comparison with the HOMO/LUMO energy levels of azulene, those of 1 and 4 shift downward with ΔEHOMOELUMO of -0.23/-0.18 and -0.20/-0.15 eV, respectively. The investigations of physical/chemical properties of 2/6-aryl substituted azulene derivatives will provide valuable insights for developing azulene-based organic functional molecules.

Key words: azulene, aryl substitution, proton response