Assembly of the highest connectivity Wells-Dawson polyoxometalate coordination polymer: the use of organic ligand flexibility.
Assembly of the highest connectivity Wells-Dawson polyoxometalate coordination polymer: the use of organic ligand flexibility.
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DOI：
10.1021/ic7023082
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发表时间：
2008-03
影响因子：
4.6
通讯作者：
A. Tian;J. Ying;Jun-Jun Peng-Jun;Jingquan Sha;Zhan-gang Han;Jian-Fang Ma;Z. Su;N. Hu;H. Jia
中科院分区：
文献类型：
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作者：
A. Tian;J. Ying;Jun-Jun Peng-Jun;Jingquan Sha;Zhan-gang Han;Jian-Fang Ma;Z. Su;N. Hu;H. Jia
通过调整柔性双绞线的长度，三氮唑配体和不同金属离子配位构型，四种Wells-Dawson多氧阴离子杂化化合物，[Cu 6（btp）3（P2W18O62）].3H2O（1）（btp = 1，3-双（1，2，4-三唑-1-基）丙烷），[Cu 6（btb）3（（P2W18O62）].2H2O（2），[Cu3（btb）6（P 2W 18O 62）].6H 2O（btb = 1，4-双（1，2，4-三唑-1-基）丁烷）（3）和[Cu 3（btx）5.5（P2 W18 O 62）].4H2O（btx = 1，6-双（1，2，4-三唑-1-基）己烷）（4）的合成和结构表征。在化合物1中，金属-有机基序呈现梯状链，并进一步与九配位的[P2 W18 O 62]（6-）阴离子形成三维结构.在化合物2中，金属有机基序表现出一个有趣的Cu-btb网格层，和九齿的多氧阴离子被夹在两个Cu-btb层，以构建一个3D结构。化合物3显示出（4（2）.6（2）.8（2））3D Cu-btb骨架，具有交替排列的正方形和六边形通道。六齿多氧阴离子仅结合到六边形通道中。在化合物4中，存在两组（6（1）.10（2））2（6（1）.8（2）.10（3））3D Cu-btx骨架以产生2重互穿结构，五齿多氧阴离子插入其中以构建3D结构。结构分析表明，柔性双三唑配体的长度和金属离子的配位几何构型对该系列化合物的结构有协同影响。据我们所知，它们具有迄今为止Wells-Dawson聚氧乙烯酸盐配位聚合物的最高连接性。
Through tuning the length of flexible bis(triazole) ligands and different metal ion coordination geometries, four Wells-Dawson polyoxoanion-based hybrid compounds, [Cu 6(btp) 3(P 2W 18O 62)].3H 2O ( 1) (btp = 1,3-bis(1,2,4-triazol-1-y1)propane), [Cu 6(btb) 3((P 2W 18O 62)].2H 2O ( 2), [Cu 3(btb) 6(P 2W 18O 62)].6H 2O (btb = 1,4-bis(1,2,4-triazol-1-y1)butane) ( 3), and [Cu 3(btx) 5.5((P 2W 18O 62)].4H 2O (btx = 1,6-bis(1,2,4-triazol-1-y1)hexane) ( 4), were synthesized and structurally characterized. In compound 1, the metal-organic motif exhibits a ladder-like chain, which is further fused by the ennead-dentate [P 2W 18O 62] (6-) anions to construct a 3D structure. In compound 2, the metal-organic motif exhibits an interesting Cu-btb grid layer, and the ennead-dentate polyoxoanions are sandwiched by two Cu-btb layers to construct a 3D structure. Compound 3 exhibits a (4 (2).6 (2).8 (2)) 3D Cu-btb framework with square and hexagonal channels arranged alternately. The hexa-dentate polyoxoanions incorporate only into the hexagonal channels. In compound 4, there exist two sets of (6 (1).10 (2)) 2(6 (1).8 (2).10 (3)) 3D Cu-btx frameworks to generate a 2-fold interpenetrated structure into which the penta-dentate polyoxoanions are inserted to construct a 3D structure. The structural analyses reveal that the length of flexible bis(triazole) ligands and metal ion coordination geometries have a synergic influence on the structures of this series. To our knowledge, they have the highest connectivity for the Wells-Dawson polyoxometalate coordination polymers to date.