Thermal expansion behaviors of Mn(Ⅱ)-pyridylbenzoate frameworks based on metal-carboxylate chains  

作　　者：ZHOU HaoLong Li Mian LI Dan ZHANG JiePeng CHEN XiaoMing 

机构地区：[1]MOE Key Laboratory of Bioinorganic and Synthetic Chemistry,School of Chemistry and Chemical Engineering, Sun Yat-Sen University [2]Department of Chemistry, Shantou University

出　　处：《Science China Chemistry》2014年第3期365-370,1-3,共6页中国科学（化学英文版）

基　　金：supported by the National Basic Research Progrem of China(2012CB821706);the National Natural Science Foundation of China(21121061 and 21225105)

摘　　要：Solvothermal reactions of MnCl2with pyridylbenzoic acids gave three-dimensional metal-carboxylate frameworks(MCFs),named MCF-34,MCF-43,and MCF-44,based on one-dimensional Mn-carboxylate chains.The crystal structure,stability,porosity,and framework flexibility of the new compound MCF-44 were studied in detail and compared with its analogs.Depending on their shapes and the bridging angles of the ligands,these compounds possess different network connectivities and porosities.Considering the pyridylbenzote ligands and Mn(II)ions as,respectively,3-and 6-connected nodes,they resemble either the anatase(ant)or rutile(rtl)polymorph of TiO2.Variable-temperature single-crystal X-ray diffraction studies revealed large thermal expansion coefficients for these compounds,which are probably related to the relatively flexible edge-sharing polyhedral structure of their Mn-carboxylate chains.Interestingly,the new compound MCF-44,with its highly porous rtl structure exhibits the largest thermal expansion coefficienct among the coordination polymers reported so far.Solvothermal reactions of MnCl2with pyridylbenzoic acids gave three-dimensional metal-carboxylate frameworks（MCFs）,named MCF-34,MCF-43,and MCF-44,based on one-dimensional Mn-carboxylate chains.The crystal structure,stability,porosity,and framework flexibility of the new compound MCF-44 were studied in detail and compared with its analogs.Depending on their shapes and the bridging angles of the ligands,these compounds possess different network connectivities and porosities.Considering the pyridylbenzote ligands and Mn（II）ions as,respectively,3-and 6-connected nodes,they resemble either the anatase（ant）or rutile（rtl）polymorph of TiO2.Variable-temperature single-crystal X-ray diffraction studies revealed large thermal expansion coefficients for these compounds,which are probably related to the relatively flexible edge-sharing polyhedral structure of their Mn-carboxylate chains.Interestingly,the new compound MCF-44,with its highly porous rtl structure exhibits the largest thermal expansion coefficienct among the coordination polymers reported so far.

关 键 词：coordination polymer thermal expansion framework flexibility TOPOLOGY 

分 类 号：O627.7[理学—有机化学]