含1,3,5-三-((4-吡啶)-1,2-乙烯基)苯的配位聚合物的合成、结构及性质  

Synthesis,Structures and Properties of Six Coordination Polymers of 1,3,5-Tri-4-pyridyl-1,2-ethenylbenzene

作　　者：田千 张建国 倪春燕[1] 杨战永 姚志刚 张敏杰 郎建平[1] TIAN Qian;ZHANG Jian-Guo;NI Chun-Yan;YANG Zhan-Yong;YAO Zhi-Gang;ZHANG Min-Jie;LANG Jian-Ping(Suzhou Key Laboratory of Precision Transformation of Resource Molecules,College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou,Jiangsu 215123,China;Analysis and Testing Center,Soochow University,Suzhou,Jiangsu 215123,China)

机构地区：[1]苏州大学材料与化学化工学部,苏州市资源分子精准转化重点实验室,苏州215123 [2]苏州大学分析测试中心,苏州215123

出　　处：《无机化学学报》2020年第6期1063-1071,共9页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21531006,21773163);苏州市资源分子精准转化重点实验室(No.SZS201905)资助项目。

摘　　要：用三烯烃三吡啶配体1,3,5三-((4-吡啶)-1,2-乙烯基)苯(tpeb)和M(NO3)2(M=Co,Ni,Zn,Cd)以及4种不同的有机羧酸(3,5-二溴苯甲酸(3,5-HDBB)、2,5-噻吩二羧酸(2,5-H2TDC)、2,5-呋喃二羧酸(2,5-H2FDC)、2,5-二溴对苯二甲酸(2,5-H2DBTP))进行溶剂热反应,得到了[Zn(tpeb)(3,5-DBB)2]n(1)、[Co2(tpeb)2(2,5-TDC)2]n(2)、[Co2(tpeb)2(2,5-FDC)2]n(3)、[Co(tpeb)(2,5-DBTP)]n(4)、[Ni(tpeb)(2,5-DBTP)]n(5)、[Cd(tpeb)0.5(2,5-DBTP)]n(6)六个配位聚合物。对配合物1~6分别进行了单晶X射线衍射、粉末X射线衍射、红外、元素分析、热重、荧光等结构表征。配合物1~6结构独特且多样。配合物1是由[Zn(3,5-DBB)2]单元通过配体tpeb桥联构筑的一维zigzag链状结构;配合物2和3是由一维梯状[Co(tpeb)]n链分别与2种不同的五元杂环二取代羧酸桥联构筑而成的二维双层结构;配合物4和5均是由一维[M(2,5-DBTP)]n(M=Co,Ni)链通过tpeb交叉连接而成的三维网络结构;配合物6则是由二维的[Cd(2,5-DBTP)]n层状结构通过tpeb连接而成的三维互穿拓扑网络结构。配合物1~6的热稳定性较好,它们在固态时表现出不同的荧光性质。Reactions of the tri-olefinic tri-pyridyl ligand 1,3,5-tri-4-pyridyl-1,2-ethenylbenzene(tpeb)with four metal nitrates M(NO3)2(M=Co,Ni,Zn,Cd)and various carboxylic acids including 3,5-dibromobenzoic acid(3,5-HDBB),2,5-thiophenedicarboxylic acid(2,5-H2TDC),2,5-furandicarboxylic acid(2,5-H2FDC)and 2,5-dibromoterephthalic acid(2,5-H2DBTP)gave rise to six coordination polymers,namely[Zn(tpeb)(3,5-DBB)2]n(1),[Co2(tpeb)2(2,5-TDC)2]n(2),[Co2(tpeb)2(2,5-FDC)2]n(3),[Co(tpeb)(2,5-DBTP)]n(4),[Ni(tpeb)(2,5-DBTP)]n(5)and[Cd(tpeb)0.5(2,5-DBTP)]n(6).Complexes 1~6 were characterized by elemental analysis,infrared spectrum(IR),thermogravimetric analysis(TGA),powder X-ray diffraction(PXRD)and single crystal X-ray diffraction.Complexes 1~6 show rich structure varieties from one-dimensional(1D)to three-dimensional(3D).Compound 1has a 1D zigzag chain structure in which the[Zn(3,5-DBB)2]units are interconnected by tpeb ligands.Complexes2 and 3 contain a similar two-dimensional(2D)double-layer network assembled from 1D ladder chains of[Co(tpeb)]nbridged by 2,5-TDC or 2,5-FDC.Complexes 4 and 5 hold a 3D framework constructed by bridging 1D chains of[M(2,5-DBTP)]n(M=Co,Ni)with tpeb ligands.Compound 6 contains 2D[Cd(2,5-DBTP)]nnetworks,which are interlinked by tpeb bridges,forming a unique 3D framework.Complexes 1~6 have good thermal stability,and exhibit various fluorescence emissions in the solid state.CCDC:1981275,1;1902623,2;1902624,3;1902626,4;1902627,5;1981276,6.

关 键 词：配位聚合物 晶体结构 三烯烃三吡啶配体 荧光性质 

分 类 号：O614.812[理学—无机化学] O614.813[理学—化学]