Chinese Journal of Organic Chemistry >
Design, Synthesis and Properties of 2/6-Aryl Substituted Azulene Derivatives
Received date: 2018-05-02
Revised date: 2018-06-03
Online published: 2018-06-06
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 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 ΔEHOMO/ΔELUMO 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
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
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