3d-4f异金属修饰的缺位Lindqvist型同多酸化合物的合成与表征

Synthesis and characterization of a new 3d-4f heterometallic lacunary Lindqvist isopolytungstate derivative

在水热条件下,成功合成了一例新的异金属修饰的有机-无机杂化型多金属同多酸簇合物[Cu(en)_2(H_2O)]_4[Ce(W_5O_(18))_2]·4H_2O(1)(en=乙二胺),采用X射线单晶衍射、元素分析、X射线粉末衍射及热重分析对化合物进行了结构分析和基本表征.化合物1属于单斜晶系,P2_1/c空间群,单胞参数为a=2.736 1(2)nm,b=1.452 52(7)nm,c=1.634 53(9)nm,β=97.153(6)°.结构解析表明,化合物1中的中心离子Ce^(4+)与两个同多酸簇块的O原子结合形成八配位的四方反棱柱体,并通过游离的及支撑的[Cu(en)_2(H_2O)]^(2+)进行修饰.值得注意的是,化合物1是首例基于{W_5O_(18)}型同多酸簇块的Cu-Ce异金属修饰型有机-无机杂化的孤立结构.

A new organic-inorganic hybrid [W_5O_（18）]-based TM-Ln heterometallic isopolyoxotungstate[Cu（en）_2（H_2O）]_4[Ce（W_5O_（18））_2]·4H_2O（1）（Ln=lanthanide,TM=transition metal,en=1,2-ethylenediamine） has been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction,elemental analysis,powder X-ray diffraction as well as thermogravimetric analysis.Compound 1 belongs to Monoclinic and P2_1/c space group,and the cell parameters are a=2.736 1（2） nm,b=1.452 52（7） nm,c=1.634 53（9） nm,β=97.153（6） °.The Structural analysis shows that CeⅣcation coordinated with O atoms from two [W_5O_（18）]_6-units,forming distorted square antiprism geometry,and was defined by copper-en cations.Notably,compound 1 represents the first discrete W_5O_（18）-containing TM-Ln heterometallic isopolyoxotungstate.