高等学校化学学报

高等学校化学学报 ›› 2006, Vol. 27 ›› Issue (4): 711.

• 研究论文 • 上一篇    下一篇

水杨醛缩乙二胺双席夫碱及其Ni(Ⅱ) 配合物的电子结构和非线性光学性质的INDO/CI研究

颜力楷1, 苏忠民1,2, 仇永清1, 朱东霞1,3, 王悦2,3, 王荣顺1, 任爱民2, 封继康2   

  1. 1. 东北师范大学化学学院功能材料化学研究所, 长春 130024; 2. 吉林大学理论化学研究所,
    理论与计算化学国家重点实验室, 3. 吉林大学教育部超分子结构与材料重点实验室, 长春 130023
  • 收稿日期:2005-04-12 出版日期:2006-04-10 发布日期:2006-04-10
  • 通讯作者: 苏忠民(1960年出生)， 男， 博士， 教授， 博士生导师， 从事量子化学和功能材料化学研究. Email: zmsu@nenu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号： 20373009)资助

INDO/CI Studies on Electronic Structure and Nonlinear Optical Properties
of Bis(salicylaldiminatio) Schiff Base Compounds and
Their Ni(Ⅱ) Complexes

YAN Li-Kai1, SU Zhong-Min1,2*, QIU Yong-Qing1, ZHU Dong-Xia1,3, WANG Yue2,3, WANG Rong-Shun1, REN AiMin2, FENG Ji-Kang2   

  1. 1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024;
    2. Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry;
    3. Key Laboratory for Supramolecular Structure and Materials of Ministry of Education,
    Jilin University, Changchun 130023, China
  • Received:2005-04-12 Online:2006-04-10 Published:2006-04-10
  • Contact: SU Zhong-Min,E-mail: zmsu@nenu.edu.cn

PDF (PC)

被引次数

37

摘要：

采用量子化学ab initio HF方法, 在6.31G(d)基组水平上， 对水杨醛缩乙二胺类双席夫碱及其Ni配合物体系进行几何构型优化. 以优化的稳定构型为基础, 利用INDO/CI方法计算体系的电子光谱, 同时用ZINDO.SOS方法给出该系列分子二阶(βijk)和三阶(γijkl)非线性光学系数. 计算结果表明, 共轭性增强有助于增大分子的二阶及三阶非线性光学系数, 双席夫碱化合物1的β和γ值分别为35.54×10-30和-1.20×10-34 esu, 而共轭桥为萘环的化合物4的β和γ值分别为54.22×10-30和2.00×10-34 esu, 端部引入苯并环的化合物5的β和γ值增加幅度更大. 对应的金属Ni(Ⅱ)配合物的β值增加较明显, 为配体的1.7~10.8倍, γ值也有不同程度的增加.

关键词: 双席夫碱; 配合物; 非线性光学性质; 从头算HF方法； ZINDO-SOS

Abstract:

The geometries of bis(salicylaldiminatio) Schiff base compounds and their Ni(Ⅱ) complexes were optimized by using ab initio HF method at the 6.31G(d) basis set. On the basis of the stable structures, the electronic spectra of these systems were studied by INDO/CI method. The nonlinear optical(NLO)coefficients were calculated by ZINDO/SOS method. The results show that the hyperpolarizabilities(β and γ) were increased with the increase of the conjugated range. The β and γ values of compound 1 are 35.54×10-30 esu and -1.20×10-34 esu, respectively, but β and γ values of compound 4 in which the conjugated bridge is naphthyl ring are 5422×10-30 esu and -2.00×10-34 esu, respectively. Compound 5 in which the phenyl ring is introduced from the terminal has the largest NLO coefficient. The value of β increased significantly by introducing Ni(Ⅱ) into the complexes, the β value of complexes are 1.7—10.8 times larger than that of other compounds, the value of γ also increased to a different extent.

中图分类号: 

TrendMD: