基于3,4⁃乙撑二氧基噻吩环配体的铜/锌配合物的合成、晶体结构及性质  

Syntheses,Crystal Structure and Properties of Cu/Zn Complexes Based on 3,4⁃Ethylenedioxythiophene Ring Ligand

作　　者：韦文厂 刘峥[1] 魏润芝 唐群[1] 梁楚欣 张淑芬[2] WEI Wen-Chang;LIU Zheng;WEI Run-Zhi;TANG Qun;LIANG Chu-Xin;ZHANG Shu-Fen(College of Chemical and Biological Engineering,Guilin University of Technology,Guangxi Key Laboratory of Electrochemical and Magneto-chemical Functional Materials,Guilin,Guangxi 541004,China;Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian,Liaoning 116024,China)

机构地区：[1]桂林理工大学化学与生物工程学院,电磁化学功能物质广西区重点实验室,桂林541004 [2]大连理工大学精细化工重点实验室,大连116024

出　　处：《无机化学学报》2020年第10期1891-1898,共8页Chinese Journal of Inorganic Chemistry

基　　金：广西自然科学基金(No.2016GXNSFAA380109);国家自然科学基金(No.21501033);桂林理工大学广西有色金属隐伏矿床勘查及材料开发协同创新中心基金(No.GXYSXTZX2017-II-3);“广西特聘专家”专项经费(No.2401007012)资助项目。

摘　　要：利用3,4-乙撑二氧基噻吩-2,5-二羧酸(H2L1)为主配体,2,2′-联吡啶(L2)、4,4′-联吡啶(L3)为辅配体,分别与二水合氯化铜、氯化锌通过溶剂热反应得到配合物{[Cu2(L1)2(L2)(H2O)2(DMF)]·3H2O}n(1)(DMF=N,N-二甲基甲酰胺)和配合物{[Zn(L1)(L3)(H2O)2]·H2O}n(2)。通过X射线单晶衍射法、红外光谱、元素分析、紫外光谱、荧光光谱、热重分析等测试手段对其结构进行了表征与性质研究。单晶结构分析表明:配合物1是由L12-桥联Cu2+形成的二维层状结构,并进一步通过氢键作用形成三维网络结构。配合物2是由L12-连接Zn2+形成一维链,并进一步桥联4,4′-联吡啶形成为一维带状结构,通过配位水分子与配体氧原子的氢键作用及带与带之间的π-π堆积形成三维结构。荧光分析和热重分析结果分别表明配合物1和2均有良好的荧光性能和热稳定性。配合物1和2的最大发射波长分别为364和365 nm。Two transition metal coordination polymer materials{[Cu2(L1)2(L2)(H2O)2(DMF)]·3H2O}n(1)(DMF=N,Ndimethylformamide)and{[Zn(L1)(L3)(H2O)2]·H2O}n(2),were successfully synthesized by solvothermal method with 3,4-ethylenedioxythiophene-2,5-dicarboxylic acid(H2L1),2,2′-bipyidine(L2),and 4,4′-bipyidine(L3).The complexes were characterized by X-ray single crystal diffraction,infrared spectroscopy(IR),UV spectrum,fluorescence spectroscopy(FL)and thermogravimetric analysis(TG/DTG).The single crystal structure analysis shows that complex 1 is a two-dimensional(2D)layered structure formed by L12-ligands bridging Cu2+ions,and a three-dimensional(3D)network structure is further formed by hydrogen bonding interaction of L2 ligands.Complex 2 forms one-dimensional(1D)chain by L12-ligands connecting Zn2+ions,and further bridging L3 ligand to form 1D band structure,which is stacked to from 3D structure by the hydrogen-bonding andπ-πstacking interaction between coordination water molecules and ligand oxygen atom.The FL and TG/DTG results indicate that complexes 1 and 2 have good thermal stability and fluorescence properties.The maximum emission peaks of complexes 1 and 2 are 364 and 365 nm,respectively.CCDC:1946117,1;1946113,2.

关 键 词：配合物 3 4-乙撑二氧基噻吩-2 5-二羧酸 晶体结构 荧光性质 热稳定性 

分 类 号：O614.121[理学—无机化学] O614.241[理学—化学]