二氰基二硫纶和4,4-二甲基2,2-联吡啶镍(Ⅱ)配合物的光谱和理论研究

报道了标题配合物Ni(mnt)(dmbpy)溶液的电子光谱、粉末样品部分IR光谱及量子化学理论研究结果.PM3方法的几何优化表明,该配合物分子为平面结构,其对称性属于C2v点群,基态为自旋三重态.结合ZINDO方法的CI计算,解释了实测电子光谱,发现该配合物在可见区450～550nm存在本质上属于配体dmbpy到配体mnt2-的荷移跃迁(LL′CT).建立了解析复杂分子振动光谱的一种新方法:根据理论计算所得三维动态图象,对于每一个正则模,先给出固定不动的点,再给出关键性的振动类型.在本方法中,用符号η(X)定义了一种新的沿给定方向起伏或跳动式的振动类型.

Spectroscopic and Theoretical Studies on Nickel(Ⅱ) Complex of Maleinitriledithiolate and 4,4′-Dimethyl-2,2′-bipyridine

The electronic spectra in several solvents, complete IR spectra in powder state and quantum chemical theoretical studies of the title complex Ni(mnt)(dmbpy) were reported in this paper. Geometry optimization calculations by PM3 method show that the complex is of a planar structure with the symmetry C2vand the spin triplet as the ground state. The CIcalculations by ZINDO/S method proved that the bands (450-550 nm) in the visible region in the observed spectra belong to the charge transfer from the ligand dmbpy to another ligand mnt2-(LL'CT) essentially. Anew method for analyzing vibrational spectra of complicated molecule is established by PM3 calculations. The essential of this method is to give main fixed points and pivotal vibrational units in assignment for each normal mode. Anew vibration type describing heaving along the specified direction was defined by the symbol η(X).