八氰钨-钴异金属配合物的合成、结构和理论研究

Synthesis,Crystal Structure and Density Functional Theory Calculation on Octacyanotungstate (Ⅳ)-bridged Cobalt Complex

以八氰钨为构筑单元,与过渡金属CoⅡ离子合成了一个具有三维结构的八氰钨-钴配位聚合物Co2^Ⅱ(4-Mepy)8[W^Ⅳ(CN)8](4-Mepy=4-甲基吡啶)。通过X-射线单晶衍射、元素分析和红外光谱对标题配合物进行了结构表征。单晶结构解析表明,标题配合物属于正交晶系,Fddd空间群,部分晶体学参数为:a=13. 939(4)A,b=26. 397(7)A,c=30. 168(8)A,V=11 100(5)A^3,z=8,Dc=1. 502 g/cm^3,μ=2. 711 mm^-1,F(000)=5 056,R=0. 046 8[I>2σ(I)],wR=0. 106 2[I>2σ(I)]。Co^Ⅱ离子中心均处于压缩CoN6八面体中,Co^Ⅱ和W^Ⅳ离子通过4个CN基团与相邻异金属W彼此交替相连,形成三维网状结构。此外,基于密度泛函理论(DFT)对八氰钨-钴配位聚合物进行了量子化学计算,计算结果与实验吻合。

The title complex with the general formula Co2^Ⅱ( 4-Mepy)8[W^Ⅳ( CN)8](4-Mepy= 4-methylpyridine) has been synthesized and confirmed by single crystal X-ray diffraction,elemental analysis and infrared spectrum. Single crystal X-ray diffraction analysis reveals that it crystallizes in orthorhombic,Fddd space group with a = 13. 939( 4)A,b = 26. 397( 7)A,c = 30. 168( 8)A,V = 11 100( 5) A^3,z= 8,Dc= 1. 502 g/cm^3,μ= 2. 711 mm^-1,F( 000)= 5 056,R= 0. 046 8 and wR= 0. 106 2 with I2σ(Ⅰ).Co^Ⅱions lie in the center of the compressed CoN6 octahedron in title complex,Co^Ⅱ and W^Ⅳ ions are alternately bridged by cyano groups forming a three dimension bimetallic framework.The quantum calculation of the title complex has been performed by density functional theory method.The results of the calculation are consistent with the experiments.