基于[As_2W_(19)O_(67)(H_2O)]^(14-)构筑块的单核铥夹心型化合物的合成、结构及热稳定性  

Synthesis,structure and thermal stability of mono-thulium sandwiched compound based on [As_2W_(19)O_(67)(H_2O)]^(14-) unit

作　　者：于丽[1] 王勇[1] 万榕[1] 马鹏涛[1] 

机构地区：[1]河南大学化学化工学院,河南开封475004

出　　处：《化学研究》2015年第6期579-583,共5页Chemical Research

基　　金：河南省教育厅科学技术研究重点项目基金(14A150028)

摘　　要：以缺位结构钨酸盐K_(14)[As_2W_(19)O_(67)(H_2O)]为多酸前驱体与TmCl_3·7H_2O和2,6-吡啶二羧酸反应,采用常规水溶液合成法制得了一例单核铥夹心的多酸基稀土衍生物K_8H_3[Tm(H_2O)_2(As_2W_(19)O_(67))(H_2O)]·15H_2O(1),并通过X射线单晶衍射、红外光谱、变温红外光谱、紫外光谱、热重分析等方法对该化合物进行了测试和表征.X射线单晶衍射分析表明,化合物1属于单斜晶系,P-1空间群,晶胞参数a=1.253 44(6)nm,b=1.761 45(9)nm,c=2.114 66(11)nm,α=73.300 0(10)°,β=85.771 0(10)°,γ=89.948 0(10)°.该聚阴离子是由两个{AsW9}构筑块与{WO(H_2O)}片段和铥离子相连形成的夹心结构;用热重分析和变温红外光谱对化合物1的热性质进行了研究,结果表明,化合物1阴离子结构在400℃以内是对热稳定的.A new mono-thulium sandwiched arsenotungstate rare earth derivative K8H3[Tm（H2O）2（As2W（19）O67）（H2O）]·15H2O（1）has been synthesized by reaction of lacunary polyoxotungstrate precusor K14[As2W（19）O67（H2O）]and TmCl3·7H2O in the presence of 2,6-pyridinedicarboxylic acid in water,which was characterized by IR spectrum,variable-temperature IR spectra,UV spectrum,TG analysis and X-ray diffraction.X-ray diffraction indicates that this compound crystallizes in the triclinic P-1space group with the cell constants：a =1.253 44（6）nm,b = 1.761 45（9）nm,c = 2.114 66（11）nm,α = 73.300 0（10）°,β=85.771 0（10）°,γ = 89.948 0（10）°.The polyanion in 1 consists of one{WO（H2O）}fragment and a Tm^（3＋）ion sandwiched by two trivacant Keggin-type{AsW_9}building units.Thermal behavior of compound 1 was studied by means of thermogravimetric analysis（TGA）and varied temperature IR spectra,the result reveals that 1is thermally stable below 400 ℃.

关 键 词：多酸 砷钨酸盐 稀土衍生物 热稳定性 

分 类 号：O612.6[理学—无机化学]