7-二芳氨基香豆素类光敏染料的合成及光谱性能  

Synthesis and Spectral Property of 7-Diarylamino Coumarin Photosensitizers

作　　者：韩亮[1] 赵金鸽[1] 刘阳[1] 高建荣[1] 

机构地区：[1]浙江工业大学化学工程学院,浙江杭州310014

出　　处：《精细化工》2016年第10期1165-1170,共6页Fine Chemicals

基　　金：国家自然科学基金(21406202)~~

摘　　要：以7-二芳氨基香豆素为电子给体,联噻吩或联苯噻吩为π桥,氰乙酸为电子受体设计合成了两个"D-π-A"型香豆素类光敏染料(Ⅴ1和Ⅴ2),通过核磁共振氢谱及高分辨质谱测定,确认其化学结构,测定了其紫外-可见吸收光谱、荧光发射光谱。采用密度泛函理论-高斯密度泛函〔DFT-B3LYP/6-31G(d)〕对化合物进行几何优化,并进一步用TD-DFT方法计算得到吸收光谱和发射光谱,分析了构效关系。结果表明,与7-二苯氨基香豆素光敏染料(Ⅴ_3和Ⅴ_4)相比,7-二芴氨基香豆素光敏染料(Ⅴ_1和Ⅴ_2)的基态能级差分别由2.49 eV和2.62 eV减小至2.31 eV和2.49 eV;激发态能级差也相应减小了0.52 eV和0.42 eV;与以联苯噻吩为π桥的光敏染料(Ⅴ_2和Ⅴ_4)相比,以联噻吩为π桥的光敏染料(Ⅴ_1和Ⅴ_3)具有更好的分子平面性,最大吸收波长分别红移4nm和19 nm,发射波长则分别红移9 nm和16 nm。Two coumarin type organic photosensitizers（Ⅴ1and Ⅴ2） were synthesized with 7-diarylamino coumarin as a donor,dithiophene or phenylthiophene as a π-bridge,and cyanoacetic acid as an acceptor. Their structures were confirmed by proton nuclear magnetic resonance（1HNMR） and high-resolution massspectroscopy（HRMS） and their UV-vis absorption spectra and fluorescence emission spectra were measured. The geometric structures of these dyes were optimized using density functional theory（DFT） in conjunction with the d-polarized 6-31G（d） basis set. Time-dependent density functional theory（TD-DFT） was further used to calculate the absorption spectra and the emission spectra and the structure-property relationship was analyzed. The results showed that 7-difluorenylamino coumarin photosensitizers exhibited relatively smaller energy gap at the ground state（2. 31 eV and 2. 49 eV） than 7-diphenylamino coumarin photosensitizers（2. 49 eV and 2. 62 eV） and their energy gap of the excited state was also reduced by 0. 52 eV and 0. 42 eV,respectively. Compared with photosensitizers using phenylthiophene as a π-bridge,photosensitizers using dithiophene as a π-bridge had better molecular planarity and their maximum absorption wavelength was red-shifted by 4nm and 19 nm,respectively. And the maximum emission wavelength was red-shifted by 9 nm and 16 nm,respectively.

关 键 词：二芳氨基香豆素 联噻吩 联苯噻吩 氰乙酸 紫外-可见吸收光谱 荧光发射光谱 特种染料与颜料 

分 类 号：TQ613.7[化学工程—精细化工]