高等学校化学学报

高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (4): 676.

• 研究论文 • 上一篇    下一篇

低聚芴及其衍生物吸收和发射光谱性质的量子化学研究

王继芬1, 封继康1,2, 任爱民1, 刘晓冬1,2, 马於光3   

  1. 1. 吉林大学理论化学研究所理论化学计算国家重点实验室, 长春 130023;
    2. 吉林大学化学学院, 长春 130023;
    3. 吉林大学理论化学研究所超分子结构与材料教育部重点实验室, 长春 130023
  • 收稿日期:2003-08-09 出版日期:2004-04-24 发布日期:2004-04-24
  • 通讯作者: 封继康(1938年出生),男,教授,博士生导师,从事量子化学研究.E-mail:Jikangf@yahoo.com E-mail:Jikangf@yahoo.com
  • 基金资助:

    国家自然科学基金(批准号:90101026,20173021);国家重点基础研究发展规划基金(批准号:2002CB613406)资助

Quantum Chemical Studies of Absorption and Emission SpectrocopicProperties for Oglimeric Fluorenes and Its Derivatives

WANG Ji-Fen1, FENG Ji-Kang1,2, REN Ai-Min1, LIU Xiao-Dong1,2, MA Yu-Guang3   

  1. 1. State Key Lab of Theoretical and Computational Chemistry, Instituteof Theoretical Chemistry, Jilin University, Changchun 130023, China;
    2. College of Chemistry, Jilin University, Changchun 130023, China;
    3. Key Lab forSupramolecular Structure and Materials of Ministry of Education, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China
  • Received:2003-08-09 Online:2004-04-24 Published:2004-04-24

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被引次数

49

摘要： 用DFT/B3LYP方法对低聚物(PF)2n和(PFDBO)n(n=1—4)体系进行了全优化,计算得到两个系列低聚物的电离能PI(v,a)、电子亲和势EA(v,a)、空穴抽取能EHP和电子抽取能EEP等相关能量,并用ZINDO和TD-DFT方法计算其吸收光谱,分析了两系列总能量和HOMO-LUMO能隙随n递增的变化规律及对低聚物稳定性和光谱性质的影响,推断高聚物的发光性质.用CIS方法优化低聚物的S1激发态结构并分析其与发射光谱的关系.计算结果表明,这两个系列低聚物激发态结构中都有使所有骨架原子共平面的趋势.由于插入CH2OCH2,使PFDBO的七元环部分发生较大的扭曲(两个苯环间成42.5°±0.5°的二面角),致使有效共轭链被破坏、能带带隙变宽、吸收发射光谱波长变短.

关键词: 低聚芴, 密度泛函理论, 吸收光谱, 发光性质

Abstract: We have fully optimized the structures of the oligomers of (PF)2n and (PFDBO)n (n=1—4) using DFT/B3LYP method and calculated their PI(v,a), EA(v,a), EHP , EEP . The absorption spectra data were calculated at ZINDO and TD-DFT levels of theory. We analyzed the rules to the variation of their HOMO-LUMO energy gap with n rising and how the energy gap reflected the spectral properties of the oligomers to deduce the spectral properties of their polymers. We optimized the S1 excited geometries and studied the emission spectra. Moreover, in the excited geometries all the framework atoms in a molecule are apt to coplanar. Above all, the dramatically twisted segment of seven-membered-ring in PFDBO(dihedral angel between it′s two phenyl ring is 42.5°±0.5°), because of CH2OCH2 caused the conjugated backbone broken. So the energy gap of it is broader, which makes in the max absorption and emission wavelengths of PFDBO shorter than PF′s.

Key words: Oligomeric fluorenes, Density functional theory, Absorptive spectrum, Luminescent properties

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