氯代芳香羧酸与联吡啶配体构筑的四种稀土配合物的晶体结构、热分析和荧光性质  

Four Rare Earth Complexes with Chlorinated Carboxylic Acids and Bipyridine Ligands:Crystal Structures,Thermal Analysis and Luminescence Properties

作　　者：周孟雪 任宁 张建军 ZHOU Meng-Xue;REN Ning;ZHANG Jian-Jun(Testing and Analysis Center,Hebei Normal University,Shijiazhuang 050024,China;College of Chemistry&Material Science,Hebei Normal University,Shijiazhuang 050024,China;College of Chemical Engineering&Material,Hebei Key Laboratory of Heterocyclic Compounds,Handan University,Handan,Hebei 056005,China)

机构地区：[1]河北师范大学分析测试中心,石家庄050024 [2]河北师范大学化学与材料科学学院,石家庄050024 [3]邯郸学院化学化工与材料学院,河北省杂环化合物重点实验室,邯郸056005

出　　处：《无机化学学报》2020年第12期2349-2358,共10页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21803016)资助项目。

摘　　要：利用2种氯代芳香羧酸(3,4-二氯苯甲酸和3,5-二氯苯甲酸,分别简写为3,4-HDClBA和3,5-HDClBA)与5,5'-二甲基-2,2'-联吡啶(5,5'-DM-2,2'-bipy)配体在溶剂热或常温反应的条件下成功地合成了4种稀土配合物[Ln2(5,5'-DM-2,2'-bipy)2(3,4-DClBA)6(H2O)(C2H5OH)](Ln=Sm(1),Eu(2))和[Ln(5,5'-DM-2,2'-bipy)(3,5-DClBA)3]2(Ln=Sm(3),Eu(4))。配合物1和2是同构的,每个中心离子是八配位的扭曲四方反棱柱的几何构型,分子与分子之间通过C-H…Cl氢键和π-π堆积作用形成二维的超分子结构。配合物3的几何构型为九配位的单帽四方反棱柱体,分子与分子之间通过不同的π-π堆积作用形成二维的超分子结构。利用热重红外联用技术研究了配合物1~4的热稳定性和热分解机理。对配合物2和4进行了荧光以及荧光寿命研究,结果表明2个配合物都能发射Eu^3+离子的特征荧光。Four new complexes were successfully synthesized by solvothermal method or conventional solution method,namely[Ln2(5,5'-DM-2,2'-bipy)2(3,4-DClBA)6(H2O)(C2H5OH)](Ln=Sm(1),Eu(2))and[Ln(5,5'-DM-2,2'-bipy)(3,5-DClBA)3]2(Ln=Sm(3),Eu(4);3,4-HDClBA=3,4-dichlorobenzoic acid,3,5-HDClBA=3,5-dichlorobenzoic acid,5,5'-DM-2,2'-bipy=5,5'-dimethyl-2,2'-bipyridine).Complexes 1 and 2 are isostructure and each metal center is eight-coordinated forming a distorted square antiprismatic.Complexes 1 and 2 are connected to form 2D supermolecular structure by C-H…Cl hydrogen bonding and π-π interactions.The geometry of complex 3 is a nine coordinated distorted monocapped square antiprismatic,and the two-dimensional supramolecular structure is formed by different π-π stacking interactions between molecules.Thermogravimetric-infrared combined technology revealed the thermal stability and thermal decomposition mechanism of complexes 1~4.The fluorescence and lifetime of complexes 2 and 4 were studied.The results showed that both complexes could emit the characteristic fluorescence of Eu^3+ ions.CCDC:1939324,1;1939325,2;1939326,3.

关 键 词：稀土配合物 合成 晶体结构 热分析 荧光性质 

分 类 号：O614.337[理学—无机化学] O614.338[理学—化学]