三角形配位构型碘化亚铜配合物的合成、结构与性质

Syntheses, structures and properties of cuprous iodide complexes of triangle coordination geometry

对两个新颖的碘化亚铜配合物CuI[2-(Dpp)bp]2(配合物1,2-(Dpp)bp=二(二苯基膦)联苯)和Cu2(μ-I)2[TPP(o-OCH3)]2?CH3CN(配合物2,TPP(o-OCH3)=三(3-甲氧基苯基)膦)的合成、晶体结构和性质进行了研究。配合物1和配合物2分别表现为单核、双核碘化亚铜配合物的结构类型。在配合物1和2的晶体结构中,亚铜原子都表现为不同寻常的近乎平面的三角形配位构型,推测其原因可能是由于膦配体较大的空间位阻效应所致。两配合物都表现了良好的热稳定性,双核配合物2的热稳定性优于单核配合物1。配合物1和2的紫外-可见吸收主要来自于膦配体的π-π*电子吸收跃迁,配合物1和2的能隙值分别为3.58、3.21 eV,说明配合物1和2均属于半导体。

The syntheses,structures and properties of two new cuprous iodide complexes,CuI[2-(Dpp)bp]2(2-(Dpp)bp=2-(diphenylphosphino)-biphenyl)and Cu2(μ-I)2[TPP(o-OCH3)]2·CH3CN(TPP(o-OCH3)=tri(3-methoxyphenyl)phosphine)were studied.The complex 1(CuI[2-(Dpp)bp]2)andcomplex 2 showed structural styles of mononuclear and dinuclear cuprous iodide,respectively.In the crystal structures of complexes 1 and 2,cuprous atoms showed unusual near-planar triangle coordination geometry.This may be because of large steric-hinerance effect of phosphine ligand.The two complexes presented good thermal stability,and the thermal stability of dinuclear complex 2 was better than that of mononuclear complex 1.The UV-Vis absorption of the complexes 1 and 2 mainly came from theπ-π*electron transfer of the phosphine ligands.The band gaps of complexes 1 and 2 were 3.58 eV and 3.21 eV,respectively,indicating that the complexes belong to semiconductors.