理论研究四氮杂环庚烯噻吩衍生物光物理性质  

Theoretical study on photophysical properties of thiophine derivatives based on tetrazacyclopentazulene

作　　者：庾弘朗 才红 朱勋 谢文倩 YU Hong-lang;CAI hong;ZHU xun;XIE Wen-qian(College of Chemistry and Environmental Engineering,Hanshan Normal llniversity,Chaozhou 521041,China;School of Material Science and Engineering,Hanshan Normal University,Chaozhou 521041,China)

机构地区：[1]韩山师范学院化学与环境工程学院,广东潮州521041 [2]韩山师范学院材料科学与工程学院,广东潮州521041

出　　处：《化学研究与应用》2020年第9期1608-1614,共7页Chemical Research and Application

基　　金：国家自然科学基金项目(21701038);博士启动项目(QD20171103)。

摘　　要：本文运用密度泛函理论(DFT)研究了四氮杂环庚烯底物(M0)及其噻吩衍生物(M1~M4)的HOMO与LUMO能量、电离能(IP)、电子亲和势(EA)以及重组能(λ)。运用含时密度泛函理论(TDDFT)计算上述化合物的吸收与荧光光谱。结果表明,对于M0~M4分子,S0←→S1电子跃迁均归属于相应分子HOMO、LUMO之间的π←→π^*跃迁,S1态均为明态。引入噻吩对上述化合物的光物理性质产生深刻影响。S0←→S1电子跃迁振子强度由相对较强(M0~M1)变成最强(M2~M4)。随着噻吩环增多,计算的IP、λ值依次降低而EA值依次增大,表明相应空穴、电子的注入与传输能力依次增强。λelectron与λhole差值小(≤0.09 eV),表明空穴、电子传输平衡性好。所有计算结果暗示M3~M4分子可用作有机发光二极管(OLEDs)的空穴、电子注入和传输材料。Herein,HOMO and LUMO energies,ionization potentials(IP),electron affinities(EA)and reorganization energies(λ)of tetrazacyclopentazulene substrate(M0)and its thiophene derivatives(M1~M4)are investigated using density functional theory(DFT).The absorption and fluorescence emission of these compounds have also been calculated by time-dependent density functional theory(TDDFT).For all M0~M4 molecules,S0←→S1 electronic transitions are assigned to optically allowed π←→π^* transition between HOMO and LUMO.The addition of thiophene rings can produce a remarkable influence on the photophysical properties.The S0←→S1 transition oscillator strengths change from relative stronger(in M0~M1)to the strongest(in M2~M4).With the increasing in conjugated length,the computed IP andλvalues decrease in turn with the increase of the corresponding EA values,and this indicates that the capacity of hole and electron transport/injection increases.The differences betweenλelectron andλhole are small(≤0.09 eV),indicating that the balance between hole-transfer and electron-transfer is good.All the calculated results suggest that M3~M4 can be used as hole and electron transport/injection materials in organic light-emitting diodes.

关 键 词：海洋荧光分子 密度泛函理论 含时密度泛函 前线分子轨道 重组能 噻吩 

分 类 号：O641[理学—物理化学]