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具有不同配位结构的新型镉(II)-均苯三甲酸配位聚合物的合成、结构及荧光性质

Synthesis, structure, and fluorescence of the novel cadmium(II)-trimesate coordination polymers with different coordination architectures.

作者信息

Dai Jing-Cao, Wu Xin-Tao, Fu Zhi-Yong, Cui Chuan-Peng, Hu Sheng-Min, Du Wen-Xin, Wu Li-Ming, Zhang Han-Hui, Sun Rui-Qing

机构信息

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.

出版信息

Inorg Chem. 2002 Mar 25;41(6):1391-6. doi: 10.1021/ic010794y.

Abstract

Three novel complexes, Cd3tma213H2O (1), Cd3tma2dabco2H2O (2), and Cd3Htma38H2O (3) (tma = trimesate), of cadmium(II)-trimesate coordination polymers are obtained from hydrothermal reaction. 1 (C18H32O25Cd3) crystallizes in the monoclinic C2/c space group [a = 18.985(2) A, b = 7.3872(6) A, c = 20.432(2) A, = 97.1660(10), and Z = 4]. 2 (C24H22N2O14Cd3) crystallizes in the monoclinic P2(1)/c space group [a = 10.1323(2) A, b = 19.5669(5) A, c = 13.15880(10) A, = 108.9810(10), and Z = 4]. 3 (C27H28O26Cd3) belongs to the trigonal P31c space group [a = 15.7547(3) A, b = 15.7547(3) A, c = 7.93160(10) A, and Z = 2]. The Cd(II) centers in the three complexes are bridged by tma ligands in the coordination fashion of unidentate, bridging unidentate, bidentate, chelating bis-bidentate, chelating/bridging bis-bidentate, or chelating/bridging bidentate to form the T-shaped molecular bilayer motif for 1, chicken-wire-like motif for 2, and honeycomb-like porous structure for 3, respectively, in which the T-shaped molecular bilayer motif and chicken-wire-like motif are further interlinked in interdigitating or alternating fashion to construct the different coordination architectures. These three complexes exhibit strong fluorescent emission bands at 355 nm (lambda(ex) = 220 nm) for 1, 437 nm (lambda(ex) = 365 nm) for 2, and 353 nm (lambda(ex) = 218 nm) for 3 in the solid state at room temperature.

摘要

通过水热反应得到了三种新型的镉(II)-均苯三甲酸配位聚合物配合物,即Cd3tma2·13H2O(1)、Cd3tma2·dabco·2H2O(2)和Cd3Htma3·8H2O(3)(tma = 均苯三甲酸)。1(C18H32O25Cd3)结晶于单斜晶系C2/c空间群[a = 18.985(2) Å,b = 7.3872(6) Å,c = 20.432(2) Å,β = 97.1660(10)°,Z = 4]。2(C24H22N2O14Cd3)结晶于单斜晶系P2(1)/c空间群[a = 10.1323(2) Å,b = 19.5669(5) Å,c = 13.15880(10) Å,β = 108.9810(10)°,Z = 4]。3(C27H28O26Cd3)属于三方晶系P31c空间群[a = 15.7547(3) Å,b = 15.7547(3) Å,c = 7.93160(10) Å,,Z = 2]。三种配合物中的Cd(II)中心通过均苯三甲酸配体以单齿、桥连单齿、双齿、螯合双齿、螯合/桥连双齿或螯合/桥连双齿的配位方式桥连,分别形成1的T形分子双层结构、2的鸡笼状结构和3的蜂窝状多孔结构,其中T形分子双层结构和鸡笼状结构进一步以交错或交替的方式相互连接,构建出不同的配位结构。这三种配合物在室温固态下分别在355 nm(λex = 220 nm)、437 nm(λex = 365 nm)和353 nm(λex = 218 nm)处表现出强荧光发射带。

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