高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (1): 155.

• 研究论文 • 上一篇    下一篇

含二茂铁双Schiff碱配体及其Ni(II)配合物电子光谱和二阶非线性光学性质的密度泛函理论研究

李孝娟,孙世玲,刘艳,赵海波,刘春光,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:2010-08-24 修回日期:2010-09-28 出版日期:2011-01-10 发布日期:2010-12-11
  • 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(批准号: 20873017)资助.

DFT Studies on Electronic Spectra and Second\|order Nonlinear Optical Properties of Schiff Base Ligands Containing Ferrocene and Their Ni(Ⅱ) Complexes

LI Xiao-Juan, SUN Shi-Ling, LIU Yan, ZHAO Hai-Bo, LIU Chun-Guang, QIU Yong-Qing*   

  1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China
  • Received:2010-08-24 Revised:2010-09-28 Online:2011-01-10 Published:2010-12-11
  • Contact: QIU Yong-Qing E-mail:qiuyq466@nenu.edu.cn
  • Supported by:

    国家自然科学基金(批准号: 20873017)资助.

摘要: 采用密度泛函理论(DFT) B3LYP方法,对含二茂铁双Schiff碱配体和Ni(II)配合物的几何构型进行优化。在得到稳定构型基础上,采用TD-B3LYP方法计算配合物的电子光谱,并结合有限场(FF)方法研究了配体和配合物的极化率和二阶非线性光学(NLO) 性质。结果表明:配体中引入Ni(II)形成配合物后,极化率 值变化不大,增加桥的共轭性或者加入吸电子取代基 值均增大。与配体相比,配合物的二阶NLO系数均增大。双键桥连双Schiff碱配体的 值比单键桥连双Schiff碱配体的 值大较多,而单、双键桥连双Schiff碱配合物的 值接近。二茂铁基团在配体和配合物中的作用不同,在配体中二茂铁有一定的吸电子性,而在配合物中表现出给电子性。

关键词: Schiff碱配体, 金属配合物, 二阶NLO性质, DFT

Abstract: The geomertrical structures of Schiff base ligands containing ferrocene and their Ni(II) complexes were optimized by using density functional theory(DFT) B3LYP method. On the basis of the stable structures, the electronic spectrum of complexes were calculated by TD-B3LYP method. The polarizability and second-order nonlinear optical (NLO) properties of ligands and complexes were investigated by combining with the finite-field (FF) method. The results show that the values do not change significantly from ligands to their Ni(II) complexes, but enhanced by increasing the conjugation bridge and adding withdrawing-electron substituent groups. Moreover, compared with ligands, all complexes have a larger second-order NLO coefficients. The values of the double bond bridge Schiff base ligands are much larger than the single bond bridge ones, but the values of the double bond bridge Schiff base complexes are close to the single bond bridge Schiff base complexes. In addition, ferrocenyl groups have different roles in ligands and complexes, acting as an accepter in ligands but a donor in complexes.

Key words: Schiff base ligand, Metal complexes, Second-order NLO properties, DFT

TrendMD: