DFT Studies on Second-order Nonlinear Optical Properties of a Series of Axially Substituted Bis（salicylaldiminato） Zinc（II） Schiff-base Complexes  

作　　者：LIU Chunguang ZHANG Dingfan GAO Mingli LIU Shuang 

机构地区：[1]College of Chemical Engineering, Northeast Dianli University, Jilin 132012, P. R. China [2]Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China

出　　处：《Chemical Research in Chinese Universities》2015年第4期597-602,共6页高等学校化学研究（英文版）

基　　金：Supported by the National Natural Science Foundation of China（No.21373043）, the Chinese Postdoctoral Science Founda- tion（No.2013M540261）, the Scientific Research Fund for Doctor of Northeast Dianli University, China（No.BSJXM-201110） and the Innovation Fund for Graduate Student of Northeast Dianli University, China.

摘　　要：Coordination of an axial ligand to metal center to enhance the second-order nonlinear optical（NLO） re- sponse of a two-dimensional bis（salicylaldiminato） zinc（II） Schiff-base complex is an unprecedented model. The second-order NLO responses of a series of axially substituted bis（salicylaldiminato） zinc（II） Schiff-base complexes were explored according to the finite field（FF） method at CAM-B3LYP/6-31＋G（d） level（LANL2DZ basis set for metal atoms）. The results show that the second-order NLO properties can be effectively tuned by exchanging the do- nor and accepter of the axial ligand and extending the length of the conjugated bridge along the axial direction. A system involving the electron acceptor along the appropriate direction has a large three-dimensional second-order NLO response. Meanwhile, time dependent density functional theory（TD-DFT） method was employed to calculate the physical parameters of excited states. The results show that the Y- and Z-polarized transitions of the zinc（II） Schiff-base complex are the first and second excited states, respectively, and have a low-lying excited energy. Al- though the X-polarized transition has a high excited energy, the large oscillator strength indicates that it will signifi- cantly contribute to the second-order NLO response.Coordination of an axial ligand to metal center to enhance the second-order nonlinear optical（NLO） re- sponse of a two-dimensional bis（salicylaldiminato） zinc（II） Schiff-base complex is an unprecedented model. The second-order NLO responses of a series of axially substituted bis（salicylaldiminato） zinc（II） Schiff-base complexes were explored according to the finite field（FF） method at CAM-B3LYP/6-31＋G（d） level（LANL2DZ basis set for metal atoms）. The results show that the second-order NLO properties can be effectively tuned by exchanging the do- nor and accepter of the axial ligand and extending the length of the conjugated bridge along the axial direction. A system involving the electron acceptor along the appropriate direction has a large three-dimensional second-order NLO response. Meanwhile, time dependent density functional theory（TD-DFT） method was employed to calculate the physical parameters of excited states. The results show that the Y- and Z-polarized transitions of the zinc（II） Schiff-base complex are the first and second excited states, respectively, and have a low-lying excited energy. Al- though the X-polarized transition has a high excited energy, the large oscillator strength indicates that it will signifi- cantly contribute to the second-order NLO response.

关 键 词：Schiff base Zinc（II） complex Nonlinear optical property Axial ligand Density functional theory 

分 类 号：O635.1[理学—高分子化学] O635.2[理学—化学]