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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >pH-dependent assembly of two polyoxometalate host–guest structural isomers based on Keggin polyoxoanion templates
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pH-dependent assembly of two polyoxometalate host–guest structural isomers based on Keggin polyoxoanion templates

机译：基于Keggin多氧阴离子模板的两种多金属氧酸盐主体-客体结构异构体的pH依赖组装

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摘要

Two interesting polyoxometalate-templated host–guest compounds 1 and 2 with the same chemical formulae of [Ag_6(tpt)_4(SiW_(12)O_(40))Cl_2]·2H_2O have been obtained by hydrothermal reactions of monolacunary Keggin-type K_8[α-SiW_(11)O_(39)]·13H_2O with CH_3COOAg and tpt ligands under different pH conditions. Compounds 1 and 2 are structural isomers. In 1, the novel chair-like tetranuclear [Ag_4 (μ_3-Cl)_2]~(2+) clusters and additional Ag~+ ions are linked by tpt ligands to form a 2D double-layered structure featured with two different types of voids in the layer, and the double-layers are stacked into a 3D host supramolecular framework with 1D channels filled with Keggin [SiW_(12)O_(40)]~(4?) polyoxoanions and water molecules as guests. In 2, Ag~+ ions are linked by tpt ligands into a 3D framework of 10~3-ths topology. The most outstanding structural feature of 2 is that upon six-fold interpenetration among 10~3-ths nets there are still nanosized channels along the a axis to accommodate Keggin polyoxoanions and water molecules as guests. Compound 2 represents the first example of six-fold interpenetrating cationic networks templated with polyoxoanions. In this work, the obvious differences in structure between 1 and 2 show that hydrochloric acid solution conditions, which offer not only H~+ to regulate the pH value but also Cl~? to coordinate with Ag~+ ions, play an important role in the formation of host frameworks templated by Keggin-type polyoxoanions. The photoluminescence properties of 1 and 2 have been investigated in the solid state.
机译：通过单腔Keggin型K_8的水热反应获得了两个有趣的以多金属氧酸盐为模板的主体-客体化合物1和2，它们具有相同的化学式[Ag_6（tpt）_4（SiW_（12）O_（40））Cl_2]·2H_2O在不同pH条件下，具有CH_3COOAg和tpt配体的[α-SiW_（11）O_（39）]·13H_2O。化合物1和2是结构异构体。在1中，新型椅子状四核[Ag_4（μ_3-Cl）_2]〜（2+）团簇和其他Ag〜+离子通过tpt配体相连，形成具有两种不同类型空隙的二维双层结构在该层中，并将双层堆叠到3D主体超分子框架中，其中1D通道填充有Keggin [SiW_（12）O_（40）]〜（4？）多氧阴离子和水分子作为来宾。在2中，Ag〜+离子通过tpt配体连接到10〜3th拓扑的3D框架中。 2的最突出的结构特征是，在10到3秒的网中互穿六倍后，沿a轴仍存在纳米级通道，以容纳Keggin聚氧阴离子和水分子作为客体。化合物2代表以聚氧阴离子为模板的六重互穿阳离子网络的第一个例子。在这项工作中，在1和2之间存在明显的结构差异，表明盐酸溶液条件不仅提供H〜+来调节pH值，而且还提供Cl〜?。与Ag〜+离子配位，在Keggin型聚氧阴离子为模板的宿主骨架的形成中起重要作用。已经研究了固态的1和2的光致发光特性。

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