马来腈二硫纶·邻菲咯啉镍(II)配合物的电子光谱和理论研究  

Electronic Spectra and Theoretical Studies on Nickel(II) Complex of Maleinitriledithiolate and 1,10-Phenanthroline

作　　者：甘雄 谢音[1] 任小明[1] 沈玉芳[1] 彭正合[1] 周运鸿[1] 

机构地区：[1]武汉大学化学与分子科学学院

出　　处：《化学学报》2005年第14期1307-1312,i003,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.29771025;29701003);南京大学配位化学国家重点实验室研究基金资助项目.

摘　　要：测量了标题配合物Ni(mnt)(phen)在多种介质中的电子吸收光谱和发射光谱,使用密度泛函理论的B3LYP方法和分子轨道理论的PM3方法研究了其气态分子几何构型、电子结构和成键,用ZINDO/S方法通过多组态的组态相互作用(CI)计算解释了实验光谱.结果表明:该配合物分子为平面结构,对称性属于点群C2v,基态为自旋三重态,配位键Ni—N和Ni—S为典型的共价结合,Ni的3d电子反馈效应较显著;可见区的吸收带和发射带(对应于基态电子组态到较低能量激发态组态的跃迁)本质上属于配体phen到mnt2-的荷移跃迁(LL′CT),紫外区的吸收带本质上属于配体的π→π*跃迁.The UV-vis absorption spectra of the title complex Ni(mnt)(phen) in twelve solvents and its fluorescence emission spectra in four solvents were reported in this paper. The molecular geometry and elec-tronic structure for the complex in the gas phase were studied by using the PM3 method of the MOT and B3LYP method of the DFT. The observed spectra were explained by the CI calculations of multi-configurations from the ZINDO/S method of the MOT. The result shows that the gaseous molecule of the complex is of a planar structure with the symmetry belonging to point group C2v, and its ground state is the spin triplet state. The coordination bonds Ni—N and Ni—S are typically covalent bond, and the feed-back effect of the 3d electrons of nickel atom is respectably obvious. The absorption and emission bands of the complex at visible region are originated from the charge transfer transitions from ligand phen to the other ligand mnt2? (LL′CT), and the absorption bands at ultraviolet region are from π→π* transitions of the ligands.

关 键 词：镍(Ⅱ)配合物 理论研究 电子光谱 邻菲咯啉 二硫纶 B3LYP方法 电子吸收光谱 分子几何构型 分子轨道理论 密度泛函理论 组态相互作用 PM3方法 ZINDO 自旋三重态 发射光谱 多种介质 电子结构 平面结构 反馈效应 3d电子 phen 

分 类 号：O641.4[理学—物理化学]