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

doi:10.6023/cjoc201805004

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

Articles

薁2/6-位芳基取代的模型化合物的设计合成及性质研究

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

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,E-mail:yangxiaodi@shutcm.edu.cn;龚和贵,E-mail:hegui_gong@shu.edu.cn;高希珂,E-mail:gaoxk@mail.sioc.ac.cn E-mail:yangxiaodi@shutcm.edu.cn;hegui_gong@shu.edu.cn;gaoxk@mail.sioc.ac.cn
基金资助:
国家自然科学基金（No.21522209）和战略性先导科技专项B类（No.XDB12010100）.

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

Gao Honglei^a,b, Yang Xiaodi^c, Xin Hanshen^b, Gao Tiezhen^b, Gong Hegui^a, Gao Xike^b

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 E-mail:yangxiaodi@shutcm.edu.cn;hegui_gong@shu.edu.cn;gaoxk@mail.sioc.ac.cn
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21522209) and the Strategic Priority Research Program (No. XDB12010100).

1. Design, Synthesis and Properties of 2/6-Aryl Substituted Azulene Derivatives.PDF(2070KB)

Abstract

Six 2/6-aryl substituted azulene derivatives 1～6 were designed and synthesised. Compounds 1～3 and 4～6 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 1～6 were studied. To investigate the molecular sturcture, absorption spectra and energy levels of compounds 1～6, density functional theory (DFT) calculations were carried out. In comparison with the UV-Vis spectra of azulene, the absorption of S₀→S₂ transition of 1～6 showed red-shift (Δλ=6～68 nm). Owing to the strong electron-donating ability of α-thiophene group, remarkable bathochromic shifts of 3 and 6 (Δλ=68 and 48 nm, respectively) were obseved. The fluorescence spectra revealed that 4 (?_F=0.082) has the highest fluorescence quantum yield of 1～6, 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 ΔE_HOMO/ΔE_LUMO 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

Cite this article

Gao Honglei, Yang Xiaodi, Xin Hanshen, Gao Tiezhen, Gong Hegui, Gao Xike. Design, Synthesis and Properties of 2/6-Aryl Substituted Azulene Derivatives[J]. Chin. J. Org. Chem., 2018, 38(10): 2680-2692.

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薁2/6-位芳基取代的模型化合物的设计合成及性质研究

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

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