2,5位双侧基取代对聚对苯撑乙炔低聚物光学性质调制作用  

The 2,5-bis-Substitution Modulation to the Optical Properties of Poly(p-Phenylene-Ethynylene) Oligomers

作　　者：张伊娜 王素凡[1] 黄玉成[1] 周涛[1] ZHANG Yina, WANG Sufan＊, HUANG Yucheng and ZHOU Tao(College of Chemistry and Materials Science, Anhui Normal University, Anhui, Wuhu 24100)

机构地区：[1]安徽师范大学化学与材料科学学院

出　　处：《计算机与应用化学》2018年第2期126-136,共11页Computers and Applied Chemistry

基　　金：国家自然科学基金(No.21373012)资助

摘　　要：利用密度泛函理论方法,分别以氰基、羧基和氨基、羟基典型的小分子推拉电子基团为例,对2、5位双侧基取代对聚对苯撑乙炔低聚物（n=1~10）吸收光谱的调制作用进行了理论预测。推拉电子基团的引入均使聚对苯撑乙炔衍生物的特征吸收发生规律性红移,红移程度与推拉电子的相对能力有关,跃迁强度的变化与基团的电荷布居相对转移程度相关。通过电子结构和跃迁轨道等激发态性质分析得出推拉电子基团对聚对苯撑乙炔轨道能的调制机理不同。可以预测侧基推拉电子基团的引入对聚对苯撑乙炔吸收光谱影响结果与基团的推拉电子能力和结构特征等因素相关,希望此结论能为聚对苯撑乙炔衍生物和类似体系光谱性质的有效调制等实验研究提供理论支持。Using the density functional theory（DFT） method, the absorption spectra of 2,5-bis-substituted poly（p-phenylene-ethynylene）（p-PPE） derivative oligomers（n=1~10） were predicted with cyano and carboxyl as the electronic acceptor groups and amino and hydroxyl as the electronic donor groups respectively. The introduction of push and pull electronic groups make the characteristic absorption wavelength of p-PPE derivative oligomers having a regular red shift, the degree of red shift is related to the relative ability of the push and pull electron groups, the transition oscillator strength is related to the degree of density transition during the electronic excitation. Through the derivatives transition orbital analysis, it is concluded that the modulation mechanism is diverse from each other for the push and pull groups impact on the transition orbital energies of the linear conjugated p-PPE. It can be predicted that the absorption spectra of 2,5-bis-substituted p-PPE derivative can be related to the ability of the push and pull groups as well as the structural characteristics of the group itself. Hopefully the results will provide theoretical support for the effective modulation and the experimental studies of p-PPE derivatives and analogue spectral properties.

关 键 词：聚对苯撑乙炔 吸收光谱 推拉电子基团 电荷布居 

分 类 号：TQ015.9[化学工程] TP391.9[自动化与计算机技术—计算机应用技术]