3D coordination networks based on supramolecular chains as building units: synthesis and crystal structures of two silver(I) pyridyldiethynides.
3D coordination networks based on supramolecular chains as building units: synthesis and crystal structures of two silver(I) pyridyldiethynides.
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DOI：
10.1021/ic702230h
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发表时间：
2008-03
影响因子：
4.6
通讯作者：
Tianle Zhang;Jianxi Kong;Yuejie Hu;Xiang-gao Meng;Hongbing Yin;Dong-Chen Hu;Changpeng Ji
中科院分区：
文献类型：
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作者：
Tianle Zhang;Jianxi Kong;Yuejie Hu;Xiang-gao Meng;Hongbing Yin;Dong-Chen Hu;Changpeng Ji
3，5-二乙炔基吡啶分别与三氟乙酸银和硝酸银反应，高产率合成了两种吡啶基二银化物[Ag 2（3，5-C2 PyC 2）.4CF3CO2Ag.4H2O]（A）和[Ag 2（3，5-C2 PyC 2）.3AgNO3.H2O]（B）。X-射线晶体学研究表明，在A中吡啶基二乙炔基团连接Ag 11簇单元生成一维超分子链作为桥连配体，其中每个乙炔基团与4个银原子相互作用.这些带有吡啶基的超分子链通过银离子连接形成波状层，这些波状层进一步通过三氟乙酸配体连接形成三维配位网络。然而，B表现出不同的结构特征，其中一个吡啶基二乙炔配体中的两个乙炔基分别与三个和四个银原子配位。这些银乙炔簇单元通过银-乙炔和亲银相互作用连接，通过在这些单元中共享银原子而导致双银链。在B中，银双链通过桥接吡啶基二乙炔基团进一步连接以形成2D网络，其通过相邻层中的银原子与吡啶基之间的Ag-N配位键相互作用以形成3D配位网络。在这两种化合物中，三氟乙酸根和三氟硝酸根呈现出不同的成键模式，表明反离子是影响超分子链和配位网络结构的重要因素。
Two silver(I) pyridyldiethynides, [Ag2(3,5-C2PyC2).4CF3CO2Ag.4H2O] ( A) and [Ag 2(3,5-C2PyC2).3AgNO3.H2O](B), were synthesized by reactions of 3,5-diethynylpyridine with silver trifluoroacetate and silver nitrate in high yield, respectively. X-ray crystallographic studies revealed that in A pyridyldiethynide groups connect Ag 11 cluster units to generate 1D supramolecular chains as bridging ligands, where each ethynide group interacts with four silver atoms. These supramolecular chains bearing pyridyl groups are linked by silver ions to form wavelike layers, which are further connected by trifluoroacetate ligands to afford a 3D coordination network. However, B exhibits a different structural feature, where two ethynide groups in one pyridyldiethynide ligand coordinate to three and four silver atoms, respectively. These silver ethynide cluster units are linked through silver-ethynide and argentophilic interactions, leading to a double silver chain by sharing silver atoms in these units. In B, the silver double chains are further connected by bridging pyridyldiethynide groups to generate 2D networks, which interact through the Ag-N coordination bonds between silver atoms and pyridyl groups in the adjacent layers to generate a 3D coordination network. In these two compounds, trifluoroacetate and nitrate groups exhibit different bonding modes, indicating that the counterion is an important factor influencing the structures of supramolecular chains and coordination networks.