物理化学学报 >> 2012, Vol. 28 >> Issue (12): 2839-2844.doi: 10.3866/PKU.WHXB201209283

理论与计算化学 上一篇    下一篇

6,12-二乙炔基茚并[1,2-b]芴系列衍生物的非线性光学性质

宋洪娟, 张梦颖, 孙秀欣, 孙世玲, 仇永清   

  1. 东北师范大学化学学院, 功能材料化学研究所, 长春 130024
  • 收稿日期:2012-06-11 修回日期:2012-09-28 发布日期:2012-11-14
  • 通讯作者: 仇永清 E-mail:qiuyq466@nenu.edu.cn
  • 基金资助:

    国家自然科学基金(21173035)和吉林省自然科学基金(20101154)资助项目

Nonlinear Optical Properties of a Series of 6,12-Diethynylindeno[1,2-b]fluorene Derivatives

SONG Hong-Juan, ZHANG Meng-Ying, SUN Xiu-Xin, SUN Shi-Ling QIU Yong-Qing   

  1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China
  • Received:2012-06-11 Revised:2012-09-28 Published:2012-11-14
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21173035) and Natural Science Foundation of Jilin Province, China (20101154).

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摘要：

采用密度泛函理论(DFT) CAM-B3LYP方法对6,12-二乙炔基茚并[1,2-b]芴系列衍生物的极化率(αs)和第二超极化率(γs)进行研究. 结果表明, 此类分子具有较大的γs值. 用乙炔基硅烷基和氧原子取代茚并[1,2-b]芴分子6,12位的氢原子后, 分子的几何构型发生改变, 进而影响其非线性光学(NLO)性质. 连接乙炔基硅烷基的分子αs值和γs值均增大, 而连接氧原子的分子αs值和γs值均减小. 茚并[1,2-b]芴环2,8位取代基R(R=H, F, CH3)的不同, 对分子的γs值也有一定的影响, R为CH3时分子的αs值和γs值均较大. 由含时密度泛函理论(TD-DFT)方法计算的吸收光谱分析可知, 与茚并[1,2-b]芴系列分子相比, 引入乙炔基硅烷基的分子共轭性增强, 最大吸收波长红移; 引入氧原子的分子几何结构扭曲, 共轭性降低, 最大吸收波长蓝移.

关键词: 茚并[1,2-b]芴衍生物, 几何构型, 非线性光学性质, 吸收光谱, 密度泛函理论

Abstract:

The polarizabilities (αs) and second hyperpolarizabilities (γs) of a series of 6,12-diethynylindeno[1,2-b]fluorene derivatives were investigated by the density functional theory CAM-B3LYP method. The calculated results indicate that these molecules possess considerably large second hyperpolarizabilities. Replacing the 6,12-hydrogen atoms on indeno[1,2-b]fluorene molecules by ethynyl silyl or oxygen atoms results in a change in the geometry of the molecular structure, which affects the nonlinear optical (NLO) properties. Introducing ethynyl silyl groups into the molecules can increase the αs and γs values, while these values decrease introducing oxygen atoms into the molecules. Also, the γs values depend on the 2, 8-disubstituted R groups (R=H, F, CH3) of the indeno[1,2-b]fluorene molecules. When R is methyl, the molecule has much larger αs and γs values. Moreover, according to time-dependent density functional theory calculations on the indeno[1,2-b]fluorene series, the maximum absorption wavelength of the ethynyl silyl derivatives display a bathochromic shift due to increasing conjugation, while a blue shift of the maximum absorption wavelengths are observed in the oxygen-substituted derivatives because the conjugation decreases as the molecular structure is distorted.

Key words: Indeno[1,2-b]fluorene derivative, Geometric configuration, Nonlinear optical property, Absorption spectrum, Density functional theory