Twelve-connected net with face-centered cubic topology: a coordination polymer based on [Cu12(mu4-SCH3)6]6+ clusters and CN- linkers.
Twelve-connected net with face-centered cubic topology: a coordination polymer based on [Cu12(mu4-SCH3)6]6+ clusters and CN- linkers.
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DOI：
10.1002/anie.200500290
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发表时间：
2005-07
影响因子：
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通讯作者：
Dan Li;Tao Wu;Xiao‐Ping Zhou;Rui Zhou;Xiao-Chun Huang
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文献类型：
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作者：
Dan Li;Tao Wu;Xiao‐Ping Zhou;Rui Zhou;Xiao-Chun Huang
近年来，金属-有机配位聚合物的拓扑网络分析已成为晶体工程研究的热点，不仅是简化复杂的超分子配位聚合物的重要工具，而且对一些具有独特性能的功能材料的合理设计也具有重要意义。[1-3]在这类配位聚合物的表征和设计方面已经投入了大量的努力O Keeffe等人通过传递性pqrs确定了5个规则网、1个准规则网和14个半规则三周期网其中，面心立方网（fcu）是唯一具有传递率1112的准规则网，配位数最高（12）。有人认为，在众多的拓扑网络中，设计合成的最重要和最合理的目标是那些具有“简单、高对称性”结构的网络虽然已知许多具有包含3 ~ 8个连接节点的不同拓扑网络的配位聚合物，但[7]合成的高连接和高对称网络的例子，如fcu，迄今尚未报道。在有机化学和配位化学中，设计和合成具有原位生成配体的新型配位聚合物也引起了人们的极大兴趣我们之前报道了CuSCN与乙腈和甲醇在溶剂热条件下的反应，得到了一种新的三维聚合物光致发光配合物{[Cu (μ3-SCH3) 2 (CN)] 2 [Cu10 (μ3-SCH3) 4 (μ4-SCH3) 2]} n，其中甲基巯基肽在原位生成。配合物含有十二核铜簇(i)，可以用α-Po简单立方网（pcu）来合理化，将十核铜簇[Cu10 (μ3-SCH3) 4 (μ4-SCH3) 2]定义为节点，将[Cu (μ3-SCH3) 2 (CN)]定义为节点
In recent years, the analysis of topological networks of metal–organic coordination polymers has been a topical area of research in crystal engineering, not only as an important tool for simplifying complicated supramolecular coordination polymers, but also in the rational design of some functional materials with unique properties.[1–3] Considerable effort has been invested in the characterization and design of such coordination polymers.[4] O Keeffe et al. identified five regular nets, one quasiregular net, and fourteen semiregular three-periodic nets by transitivity pqrs.[5] Of these nets, the face-centered cubic net (fcu) is the only quasiregular net with transitivity 1112, which exhibits the highest coordination number (12). It has been suggested that among the numerous topological nets, the most important and plausible targets for designed synthesis are those with “simple, high-symmetry” structures.[6] Although many coordination polymers with different topological networks containing 3∼ 8-connected nodes are known,[7] synthetically prepared examples of higher connected and higher symmetry nets, such as fcu, have not been reported to date. Significant interest has also arisen in organic and coordination chemistry for the design and synthesis of novel coordination polymers with ligands generated in situ.[8] We have previously reported [9] the reaction of CuSCN with acetonitrile and methanol under solvothermal conditions, which yielded a novel 3D polymeric photoluminescent complex,{[Cu (μ3-SCH3) 2 (CN)] 2 [Cu10 (μ3-SCH3) 4 (μ4-SCH3) 2]} n, in which the methyl mercaptide is generated in situ. The complex contains dodecanuclear copper (i) clusters, which can be rationalized in terms of an α-Po simple cubic net (pcu), by defining the decanuclear copper cluster [Cu10 (μ3-SCH3) 4 (μ4-SCH3) 2] as a node and [Cu (μ3-SCH3) 2 (CN)] as a