由异构苯二甲酸酯和3-(2-吡啶基)吡唑组装而成的具有一维链状结构的d(10)金属配合物：合成、结构及发光性质
d(10) Metal complexes assembled from isomeric benzenedicarboxylates and 3-(2-pyridyl)pyrazole showing 1D chain structures: syntheses, structures and luminescent properties.
作者信息
Hu Tong-Liang, Zou Ruo-Qiang, Li Jian-Rong, Bu Xian-He
机构信息
Department of Chemistry, Nankai University, Tianjin 300071, China.
出版信息
Dalton Trans. 2008 Mar 14(10):1302-11. doi: 10.1039/b716398c. Epub 2008 Jan 21.
Seven new d10 metal coordination polymers with isomeric benzenedicarboxylates and 3-(2-pyridyl)pyrazole ligands, [Zn2 L2(1,2-BDC)(H2O)]n ( 1), {[Cd2(H L)2(1,2-BDC)2] x H2O}n ( 2), [Cd(H L)(1,2-BDC)(H2O)]n (3), [Zn(H L)(1,3-BDC)(H2O) x 3H2O]n ( 4), [Cd2 L2(1,3-BDC)(H2O)]n (5), [Zn(H L)2(1,4-BDC)]n ( 6) and [Cd(H L)2(1,4-BDC)]n (7) (BDC = benzenedicarboxylate, H L = 3-(2-pyridyl)pyrazole), have been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction. Single-crystal X-ray analyses reveal that each complex takes a different one-dimensional (1D) chain structure. In 1-7, the BDCs act as bridging ligands, exhibiting rich coordination modes to link metal ions. The three BDC isomers exhibit different coordination modes: micro(1)-eta(1):eta(1)/micro(3)-eta(2):eta(1), micro(3)-eta(1):eta(2)/micro(3)-eta(2):eta(1), micro(2)-eta(1):eta(1)/micro(1)-eta(1):eta(0) and micro(1)-eta(1):eta(1)/micro(1)-eta(1):eta(0) for 1,2-BDC, micro(1)-eta(1):eta(1)/micro(1)-eta(1):eta(0) and micro(1)-eta(1):eta(0)/micro(2)-eta(2):eta(1) for 1,3-BDC, and micro(1)-eta(1):eta(0)/micro(1)-eta(0):eta(1), micro(1)-eta(1):eta(0)/micro(1)-eta(1):eta(0) and micro(1)-eta(1):eta(1)/micro(1)-eta(1):eta(1) for 1,4-BDC, respectively. In these complexes, H acts as a simple bidentate chelate ligand (in 2, 3, 4, 6 and 7), similar to 2,2'-bipyridine, or as a tridentate chelate-bridging ligand (in 1 and 5) via deprotonation of the pyrazolyl NH group and coordination of the pyrazolyl N atom to a second metal ion. The structural differences indicate that the backbone of such dicarboxylate ligands plays an important role in governing the structures of such metal-organic coordination architectures, and the chelating bipyridyl-like ligand H leads to the formation of these coordination polymers with one-dimensional structures by occupying the coordination sites of metal ions. Moreover, the photoluminescent properties of complexes were also studied in the solid-state at room temperature.
合成了七种具有异构苯二甲酸酯和3-(2-吡啶基)吡唑配体的新型d10金属配位聚合物，[Zn2 L2(1,2-BDC)(H2O)]n (1)、{[Cd2(H L)2(1,2-BDC)2] x H2O}n (2)、[Cd(H L)(1,2-BDC)(H2O)]n (3)、[Zn(H L)(1,3-BDC)(H2O) x 3H2O]n (4)、[Cd2 L2(1,3-BDC)(H2O)]n (5)、[Zn(H L)2(1,4-BDC)]n (6) 和 [Cd(H L)2(1,4-BDC)]n (7)（BDC = 苯二甲酸酯，H L = 3-(2-吡啶基)吡唑），并通过元素分析、红外光谱和X射线衍射对其进行了结构表征。单晶X射线分析表明，每个配合物都具有不同的一维(1D)链结构。在1-7中，BDCs作为桥连配体，表现出丰富的配位模式以连接金属离子。三种BDC异构体表现出不同的配位模式：对于1,2-BDC，分别为μ(1)-η(1):η(1)/μ(3)-η(2):η(1)、μ(3)-η(1):η(2)/μ(3)-η(2):η(1)、μ(2)-η(1):η(1)/μ(1)-η(1):η(0) 和 μ(1)-η(1):η(1)/μ(1)-η(1):η(0)；对于1,3-BDC，为μ(1)-η(1):η(1)/μ(1)-η(1):η(0) 和 μ(1)-η(1):η(0)/μ(2)-η(2):η(1)；对于1,4-BDC，为μ(1)-η(1):η(0)/μ(1)-η(0):η(1)、μ(1)-η(1):η(0)/μ(1)-η(1):η(0) 和 μ(1)-η(1):η(1)/μ(1)-η(1):η(1)。在这些配合物中，H作为简单的双齿螯合配体（在2、3、4、6和7中），类似于2,2'-联吡啶，或者通过吡唑基NH基团的去质子化以及吡唑基N原子与第二个金属离子的配位作用，作为三齿螯合桥连配体（在1和5中）。结构差异表明，此类二羧酸酯配体的主链在控制此类金属有机配位结构的结构中起重要作用，并且螯合的联吡啶样配体H通过占据金属离子的配位位点导致形成这些具有一维结构的配位聚合物。此外，还在室温下对配合物的固态光致发光性质进行了研究。
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