两个链状稀土配位聚合物的合成、结构及热动力学  

Synthesis,structure and thermal analysis kinetics of two chain coordination polymers for rare earth ions

作　　者：解凤霞[1] 张孝峰[1] 尹帆[1] 郭乐 赵纲 

机构地区：[1]西安工程大学环境与化学工程学院,陕西西安710048

出　　处：《纺织高校基础科学学报》2017年第3期409-416,共8页Basic Sciences Journal of Textile Universities

基　　金：陕西省教育厅专项科研计划项目(16JK1346);西安工程大学大学生创新训练项目(1690)

摘　　要：采用水热法合成两个稀土羧酸配位聚合物{Ln(H2L)(HL)(H2O)}n,{H3L=5-(对羧苄氧基)-1,3-苯二甲酸;Ln=La(1)、Nd(2)}.通过元素分析,红外光谱以及X-射线单晶衍射分析确定配合物的晶体结构.根据普适积分法对配合物的热重图谱进行热动力学分析.结果显示,两个配位聚合物属同构物,均为三斜晶系,P-1空间群.与中心稀土离子参与配位的两个5-(对羧苄氧基)-1,3-苯二甲酸配体中,一个配体中有两个羧基氧参与配位,而另一个配体只有一个羧基参与配位;配位单元LnO9的空间构型为扭曲的三帽三棱柱结构.LnO9通过羧基氧原子桥联成一维链状结构,链状结构之间通过氢键形成三维网络结构.热重分析显示配合物有很高的热稳定性,普适积分法求出配合物两次失重过程的热分解动力学的三因子,并得出决定两个配合物失重过程反应速率的关键步骤为随机成核和随后生长机理.Two complexes{Ln(H2L)(HL)(H2O)}n{H3L=5-((4-carboxybenzyl)oxy)isophthalic acid,Ln=La(1),Nd(2)}were synthesized under hydrothermal condition.The complexes were characterized by the single crystal X-ray diffraction analysis,elemental analysis,IR spectroscopy,and thermogravimetric analysis.According to the universal integral method,the TG spectra of two complexes were studied for there thermal analysis kinetics.The single crystal X-ray diffraction analysis revealedthat two complexes exhibited isomorphism.The crystals belongs to triclinic,space group P-1.There are two 5-(4′carboxyl benzyl-methoxy)isophthalic acids that coordinated with rare earth ions,but they have adopted different ways of coordination,one of the ligand has two carboxyl oxygen in coordination,and the other only has one carboxyl participate in coordination.The structure of coordination unit LnO9 is distorted three hat triprism.LnO9 is connected with oxygen atom of carboxyl to one-dimensional chain structure and the complexes presented 3Dnetwork structures by the interaction of the hydrogen bonds.TG analysis showed that complexes have very high stability.Based on the universal integral method,kinetics triplets for weightlessness process are obtained and it is the random nucleation and subsequent growth mechanism which controlled the key step of reaction rate in the process of weightlessness.

关 键 词：水热法 稀土配位聚合物 晶体结构 热分析动力学 

分 类 号：O614.81[理学—无机化学]