Citation: Gao Honglei, Yang Xiaodi, Xin Hanshen, Gao Tiezhen, Gong Hegui, Gao Xike. Design, Synthesis and Properties of 2/6-Aryl Substituted Azulene Derivatives[J]. Chinese Journal of Organic Chemistry, ;2018, 38(10): 2680-2692. doi: 10.6023/cjoc201805004 shu

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

Corresponding author: Yang Xiaodi, yangxiaodi@shutcm.edu.cn Gong Hegui, hegui_gong@shu.edu.cn Gao Xike, gaoxk@mail.sioc.ac.cn
Received Date: 2 May 2018
Revised Date: 3 June 2018
Available Online: 5 October 2018
Fund Project: the National Natural Science Foundation of China 21522209the Strategic Priority Research Program XDB12010100Project supported by the National Natural Science Foundation of China (No. 21522209) and the Strategic Priority Research Program (No. XDB12010100)

Figures(12)

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 (ϕ_F=0.082) has the highest fluorescence quantum yield of 1~6, while 1-H⁺ (ϕ_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.
- azulene,
- aryl substitution,
- proton response
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