Polymerizing cluster helicates into high-connectivity networks.
Polymerizing cluster helicates into high-connectivity networks.
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DOI：
10.1002/chem.200801300
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发表时间：
2008-10
期刊：
影响因子：
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通讯作者：
S. Zhan;Mian Li;Jin-Zhang Hou;Jia Ni;Dan Li;Xiao-Chun Huang
中科院分区：
文献类型：
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作者：
S. Zhan;Mian Li;Jin-Zhang Hou;Jia Ni;Dan Li;Xiao-Chun Huang
在不同条件下，Cu Ⅱ盐与3，5-双（4-吡啶基）吡唑（HL）的溶剂热反应得到三种不同类型的晶体化合物，即[Cu 2（Cu 5 L 6）]BF（4）·5 H2O（1 a），[Cu 2（Cu 5 L 6）]ClO（4）·5 H2O（1 B），和[Cu 7（CN）2（Cu 5 L 6）2][BF 4]3（2）. 1 a和B在乙醇和NH 3·H2O中得到，而2在甲醇和NH 3·H2O中得到。这三个配合物是通过引入新的五核铜（I）吡唑双（三螺旋）簇合物（Cu 5L 6）作为第二构建单元（SBU）而构建的，其中多达12个4-吡啶基N原子可用于进一步配位和构建高连接性拓扑网络。在1a和B中，7个4-吡啶基N原子与3个三配位的CuI原子和4个四配位的CuI原子连接，形成3，4，7-连接网络.在2中，多达11个4-吡啶基N原子与11个CuI原子配位，这导致4，10-连接的拓扑网络。2中簇节点连接性的增加与在五核簇螺旋周围原位形成的CN-阴离子桥密切相关。研究了这些化合物的发光性质。
Solvothermal reactions of CuII salts and 3,5-bis(4-pyridyl)pyrazole (HL) under various conditions gave three different types of crystalline compound, namely [Cu2(Cu5L6)]BF(4).5 H2O (1 a), [Cu2(Cu5L6)]ClO(4).5 H2O (1 b), and [Cu7(CN)2(Cu5L6)2][BF4]3 (2). 1 a and b were obtained in ethanol and NH3.H2O, whereas 2 was obtained in methanol and NH3.H2O. The three complexes were constructed by incorporating new pentanuclear copper(I) pyrazolate bis(triple helical) cluster helicates (Cu5L6) as the second building units (SBUs), in which as many as twelve 4-pyridyl N atoms are available for further coordination and construction of high-connectivity topological networks. In 1 a and b, seven 4-pyridyl N atoms are linked to three three-coordinated CuI atoms and four four-coordinated CuI atoms, which results in 3,4,7-connected networks. In 2, as many as eleven 4-pyridyl N atoms coordinate to eleven CuI atoms, which results in a 4,10-connected topological network. The increasing connectivity of the cluster nodes in 2 is closely related to the in situ-formed CN- anion bridge around the periphery of the pentanuclear cluster helicates. The luminescenct properties of these compounds were also investigated.