Li Jian-Rong, Bu Xian-He, Zhang Ruo-Hua
Department of Chemistry, Nankai University, Tianjin 300071, China.
Dalton Trans. 2004 Mar 7(5):813-9. doi: 10.1039/b316441a. Epub 2004 Feb 10.
Five novel Cd(II) coordination polymers with three structurally related flexible disulfoxide ligands, [Cd(L1)32]n (1), [Cd(L2)32(CHCl3)]n (2), [Cd(L2)(NO3)2(H2O)]n (3), [Cd2(L3)2(NO3)4]n (4) and [Cd(L3)32]n (5), where L1= 1,3-bis(phenylsulfinyl)propane, L2= 1,4-bis(phenylsulfinyl)butane and L3= 1,4-bis(ethylsulfinyl)butane, were synthesized and structurally determined by X-ray diffraction. Complex 1 has a 2D layer structure, in which part of the L1 ligands bridge the Cd(II) ions to form double-bridging chains and the other part of ligands link such chains to form a 2D framework. Complexes 2 and 5 are isomorphous, showing unusual 2D (3,6) network structures containing triangular grids. Complex 3 adopts a 2D (4,4) network formed by L2 linking the NO3- bridged (Cd-O-N-O-)n 1D zigzag chains. By contrast, is a 1D chain, in which two Cd(II) centers are bridged by mu2-O of sulfoxide groups to form a dinuclear unit, and L3 ligands link such dinuclear units to form a 1D double-bridging chain. The structural differences among such complexes show that the ligand nature and counter anions have important influences on the complex structures, which may provide a rational method for controlling the framework formation in metal-organic coordination polymers.
合成了五种新型的镉(II)配位聚合物,它们含有三种结构相关的柔性二亚砜配体,分别为[Cd(L1)32]n(1)、[Cd(L2)32(CHCl3)]n(2)、[Cd(L2)(NO3)2(H2O)]n(3)、[Cd2(L3)2(NO3)4]n(4)和[Cd(L3)32]n(5),其中L1 = 1,3 - 双(苯基亚磺酰基)丙烷,L2 = 1,4 - 双(苯基亚磺酰基)丁烷,L3 = 1,4 - 双(乙基亚磺酰基)丁烷,并通过X射线衍射确定了其结构。配合物1具有二维层状结构,其中部分L1配体桥连镉(II)离子形成双桥链,另一部分配体连接这些链形成二维框架。配合物2和5是同构的,呈现出包含三角形网格的不寻常二维(3,6)网络结构。配合物3采用由L2连接NO3 - 桥连的(Cd - O - N - O -)n一维锯齿链形成的二维(4,4)网络。相比之下,配合物4是一维链,其中两个镉(II)中心由亚砜基团的μ2 - O桥连形成双核单元,L3配体连接这些双核单元形成一维双桥链。这些配合物之间的结构差异表明配体性质和抗衡阴离子对配合物结构有重要影响,这可能为控制金属有机配位聚合物中的框架形成提供一种合理方法。