高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

二聚(2,5-噻吩乙烯撑)基态和激发态的电子结构: 桥基和芳环取代的影响

蒋洁, 孟素慈, 马晶   

  1. 南京大学化学化工学院, 介观化学教育部重点实验室, 理论与计算化学研究所, 南京 210093
  • 收稿日期:2008-03-10 修回日期:1900-01-01 出版日期:2009-02-10 发布日期:2009-02-10
  • 通讯作者: 马晶

Electronic Structures of Di(thienylene vinylene) of Ground and Excited States: Vinylene- and Ring-Substitution Effects

JIANG Jie, MENG Su-Ci, MA Jing*   

  1. Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China
  • Received:2008-03-10 Revised:1900-01-01 Online:2009-02-10 Published:2009-02-10
  • Contact: MA Jing

PDF (PC)

被引次数

2

摘要： 采用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)方法, 在B3LYP/TZVP水平下, 研究了一系列给电子基团(—NH2, —OCH3和—CH3)和吸电子基团(—CCH, —CN和—NO2)在二聚(2,5-噻吩乙烯撑)(2TV)的桥基和芳环上取代对基态和激发态电子结构的影响. 结果表明, 取代基的给/吸电子能力和取代位置对衍生物的几何结构以及吸收发射光谱均有重要影响, 其中氨基(—NH2)和硝基(—NO2)取代对2TV电子结构的影响较为显著. 此外, 对于桥基和芳环取代, 随着取代基吸电子能力的增强, 衍生物的前线分子轨道HOMO和LUMO的能级均呈逐渐降低的趋势.

关键词: 二聚(2,5-噻吩乙烯撑), 取代基效应, 电子结构, 激发态, 密度泛函理论

Abstract: The modulation of substituents on the electronic structures of ground and excited states of di(thienylene vinylene)(2TV) were theoretically investigated via the density function theory(DFT) and time-dependent density functional theory(TD-DFT) when a representative set of electron donating groups(amino, methoxy, and methyl) and withdrawing groups(acetylene, cyano, and nitro) were introduced onto vinylene and thienyl moieties, respectively. Electron-donating or withdrawing capabilities and substitution position play dominant roles in the geometries and absorption and emission transition energies of 2TV derivatives. The amino- and nitro-substituent groups exert the strongest tuning effect on electronic structures among the studied systems. As the electron-withdrawing ability of substituents increases, the energy levels of the highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital(LUMO) of resultant derivatives exhibit a progressively reducing pattern, which is held for both thienyl and vinylene functionalizations.

Key words: Di(thienylene vinylene), Substitution effect, Electronic structure, Excited state, Density functional theory

中图分类号: 

TrendMD: