Synthesis,Crystal Structure,Spectroscopic Property and Redox Behavior of Zinc(Ⅱ) Complexes Containing Oligoaniline-functionalized Terpyridine Ligands  

作　　者：邱东方 赵茜 刘克成 郭应臣 冯玉全 

机构地区：[1]College of Chemistry and Pharmacy Engineering,Nanyang Normal University

出　　处：《Chinese Journal of Structural Chemistry》2010年第10期1513-1518,共6页结构化学（英文）

基　　金：Supported by the Natural Science Foundation of Henan Province (No. 102300410221);the Natural Science Foundation of Nanyang Normal University (No. ZX2010012);Project supported by the Young Core Instructor from the Education Commission of Henan Province

摘　　要：Two novel mono-nuclear zinc（Ⅱ） complexes with oligoaniline-functionalized terpyridine ligands have been synthesized and verified by 1H-NMR,13C-NMR,Elemental Analysis （EA） and X-ray Diffraction （XRD）. The UV-vis spectra show the ligand-centered （LC） π-π＊ transitions and intra-ligand charge transfer （1ILCT） transitions,and the 1ILCT band red-shifts with the increasing number of aromatic amine groups in the ligands. Complex [Zn（L1）2]（PF6）2 with an aromatic amine group in ligand shows a strong emission peak at 523 nm in the MeCN solution at 293 K and a blue-shifted band at 517 nm in the alcoholic glass at 77 K. However,for complex [Zn（L2）2]（PF6）2 containing aniline dimer modified ligand,no apparent emission can be observed in the MeCN solution at room temperature due to a PET non-radiative decay pathway. Both of them show multiplicate redox processes based on oligoaniline and terpyridine units. The shifts of redox potentials also reflect the D-A interactions between the oligoaniline units and [Zn（TPY）2]2＋ core.Two novel mono-nuclear zinc（Ⅱ） complexes with oligoaniline-functionalized terpyridine ligands have been synthesized and verified by 1H-NMR,13C-NMR,Elemental Analysis （EA） and X-ray Diffraction （XRD）. The UV-vis spectra show the ligand-centered （LC） π-π＊ transitions and intra-ligand charge transfer （1ILCT） transitions,and the 1ILCT band red-shifts with the increasing number of aromatic amine groups in the ligands. Complex [Zn（L1）2]（PF6）2 with an aromatic amine group in ligand shows a strong emission peak at 523 nm in the MeCN solution at 293 K and a blue-shifted band at 517 nm in the alcoholic glass at 77 K. However,for complex [Zn（L2）2]（PF6）2 containing aniline dimer modified ligand,no apparent emission can be observed in the MeCN solution at room temperature due to a PET non-radiative decay pathway. Both of them show multiplicate redox processes based on oligoaniline and terpyridine units. The shifts of redox potentials also reflect the D-A interactions between the oligoaniline units and [Zn（TPY）2]2＋ core.

关 键 词：OLIGOANILINE TERPYRIDINE zinc（II） crystal structure spectroscopic property electrochemical behavior 

分 类 号：O627.23[理学—有机化学]