金属有机簇合物链为构筑单元的配位网络的组装及结构研究

项目名称： 金属有机簇合物链为构筑单元的配位网络的组装及结构研究

项目编号： No.20871049

项目类型： 面上项目

立项/批准年度： 2009

项目学科： 金属学与金属工艺

项目作者： 张天乐

作者单位： 华中科技大学

项目金额： 30万元

中文摘要： 本项目提出可利用含配位基团的乙炔基银簇合物为构筑单元，合理地构筑一类结构新颖的配位网络，并对其结构进行调控。研究结果表明这类含吡啶或羧基的乙炔基银簇合物可作为良好的双功能构筑单元用于配位网络的构筑。因此，本项目的研究结果为合理组装新型配位网络，并对其结构及功能进行有效调控提供了理论基础。 首先研究了具有不同构型的二乙炔基银簇合物，系统地探讨了配体的构型对配位网络结构的影响。结果表明配位网络的结构与配体的构型及阴离子的配位模式密切相关。 合成了四个含单乙炔基吡啶及嘧啶-银簇合物。结构研究表明由这类含单乙炔基银簇合物自组装的配位网络的结构主要由簇合物所含有的官能团的配位模式所决定。 在本项目中，首次合成了含羧基的乙炔基银簇合物，并系统地讨论了羧基的数目与配位网络结构的相关性。结果表明羧基配位模式的多样性有利于构筑高维配位网络。 同时，将相关研究拓展至构筑含孔穴的配位网络材料及低维配位聚合物。一种含吡啶及羧基的共轭有机配体用于构筑刚性、高连接的网络材料，其目的用于探索改善MOF热稳性的可能性；利用双核银配合物组装了一例结构特殊的线性配位聚合物，并研究了其成键及发光性能。

中文关键词： 银；乙炔基吡啶；羧基；配位网络；荧光

英文摘要： It was proposed that a series of new silver(I) ethynide complexes bearing functional groups could be used as building units to rationally assemble one kind of coordination networks. The obtained results demonstrate that this kind of silver complexes could serve as bifunctional building units to construct novel organometallic networks. Firstly two diethynylpyridines with different geometries have been used as ligands to synthesize silver(I) pyridyldiethynide complexes. Three new complexes have been fully characterized in order to systematically investigate the effect of the geometry of ligand on the structure of organometallic network constructed by using silver pyridyldiethynide complexes. The obtained results show that both geometry of diethynylpydidines and counter anions are important factors to control the structures of the assembled networks. Silver(I) 4-pyridylethynide and silver(I) 5-pyrimidylethynide have been synthesized and strcturally characterized in order to study the relation of the binding mode of ligand and the structure of assembled network by using silver ethynide complexes as building units. The results clearly demonstrate that the coodination mode of ligand is the key factor to control the structure of network. Recently a series of silver ethynide complexes bearing carboxylate groups have been synthesized by us for the first time. The related studies show that the versatile binding modes of carboxylate group lead to diverse and high-level architecture. Meanwhile this program has been extended to construction of porous coordination network and low-dimensional coordination polymer. One conjugated ligand containing pyridyl and carboxylate groups was designed to construct rigid and highly-connected network in order to explore the possibility to improve thermal stability of metal-organic framework (MOF), which exhibit high gas sorption and thermal stability capabilities. And one novel linear coordination polymer was constructed and theoretically studied by using dinuclear silver complexes as building blocks.

英文关键词： silver; ethynylpyridine; carboxylate; coordination network; luminescence