Lin Zhuojia, Li Yang, Slawin Alexandra M Z, Morris Russell E
EaStChem School of Chemistry, University of St Andrews, Purdie Building, St Andrews, UK KY16 9ST.
Dalton Trans. 2008 Aug 14(30):3989-94. doi: 10.1039/b802892c. Epub 2008 Jun 6.
Four new cobalt coordination polymers, (EMIm)[Co2(TMA-H)2(44bpy)3]Br 1, (EMIm)Co(TMA-H)(44bpy)2Br 2, (EMIm)[Co(TMA)(Im-H)]3 and (EMIm)2[Co(TMA)2(TED-H2)] 4, were prepared from 1-ethyl-3-methyl imidazolium bromide (EMIm-Br). All the compounds have similar two-dimensional cobalt trimesate (TMA) coordination layers but different three-dimensional supramolecular architectures that contain one of three potentially ditopic amines, 4,4'-bipyridine (44bpy), imidazole (Im-H) and triethylenediamine (TED). Two-fold interpenetration of hydrogen-bonding networks was found for 1, 2 and 4. The coordination layers of 1 and 2 are neutral while 3 and 4 have anionic molecular assemblies. The use of organic amines, that act as supramolecular bridging ligands, introduces hydrogen-bond-directing effects in the ionothermal synthesis of metal coordination polymers. Hydrogen bonding helps to align the packing between the coordination layers and control the formation of 3D supramolecular networks. In 1, hydrogen bonds between the ionic species within the channels direct the alignment of non-directional electrostatic interactions between EMIm+ and Br(-) ions, which is a rare case of a hydrogen-bond-templating effect of ionic liquids in ionothermal synthesis.
由1-乙基-3-甲基溴化咪唑（EMIm-Br）制备了四种新型钴配位聚合物，即(EMIm)[Co2(TMA-H)2(44bpy)3]Br 1、(EMIm)Co(TMA-H)(44bpy)2Br 2、(EMIm)[Co(TMA)(Im-H)]3和(EMIm)2[Co(TMA)2(TED-H2)] 4。所有化合物都具有相似的二维钴均苯三甲酸盐（TMA）配位层，但三维超分子结构不同，其中包含三种潜在的双齿胺之一，即4,4'-联吡啶（44bpy）、咪唑（Im-H）和三亚乙基二胺（TED）。发现1、2和4的氢键网络存在双重互穿。1和2的配位层是中性的，而3和4具有阴离子分子组装体。用作超分子桥连配体的有机胺在金属配位聚合物的离子热合成中引入了氢键导向作用。氢键有助于协调层之间的堆积排列并控制三维超分子网络的形成。在1中，通道内离子物种之间的氢键引导了EMIm+和Br(-)离子之间非定向静电相互作用的排列，这是离子热合成中离子液体氢键模板效应的罕见例子。
