一种含稀土阳离子的多金属氧酸盐二聚体的合成及晶体结构(英文)

以Na7[α-PW11O39].nH2O,Sm(NO3)3.6H2O和(CH3)4NCl为原料,利用常规的水溶液方法合成了一例新的2∶2型二聚单缺位Keggin结构多金属氧酸盐稀土衍生物[(CH3)4N]6[(α-PW11O39H)Sm(H2O)3]2.9H2O(1);利用X射线单晶衍射表征了其晶体结构.结果表明,该二聚体属单斜晶系,P2(1)/c空间群,晶胞参数为:a=1.300 8(10)nm,b=2.219 0(17)nm,c=2.097 0(16)nm,β=100.992(16),Z=2,R1=0.074 6,wR2=0.182 6.二聚阴离子[{(α-PW11O39H)Sm(H2O)4}2]6-由2个[α-PW11O39H]6-缺位阴离子通过2个[Sm(H2O)4]3+配离子连接形成,Sm3+离子占据[α-PW11O39H]6-阴离子的缺位位置并取八配位单四方反棱柱构型,相邻的2个单取代阴离子[α-PW11O39H]6-通过2个Sm-Ot-W桥连成二聚物.

Synthesis and crystal structure of a polyoxometalate dimmer containing rare earth cation

A new 2∶2-type dimeric polyoxometalate of rare earth derivative possessing monovacant Keggin structure,[（CH 3） 4 N ] 6 [（α-PW 11 O 39 H） Sm（H 2 O） 3 ] 2.9H 2 O（1）,was successfully synthesized by the reaction of monovacant Keggin structure Na7 [ α-PW 11 O 39 ].nH 2 O with Sm（NO 3） 3.6H 2 O and（CH 3） 4 NCl in aqueous solution.Single crystal X-ray crystallography was applied to characterize the crystal structure of as-synthesized product.Results indicate that compound 1 crystallizes in the monoclinic space group P2（1）/ c,with crystal cell parameters being a=1.300 8（10） nm,b=2.219 0（17） nm,c=2.097 0（16） nm,β =100.992（16）,Z =2,R 1 =0.074 6,and wR 2 = 0.182 6.The dimeric polyoxoanion [{（α-PW 11 O 39 H） Sm（H 2 O） 4 } 2 ] 6consists of two [ α-PW 11 O 39 H ] 6subunits linked together by two [ Sm（H 2 O） 4 ] 3＋ cations.The eight-coordinated Sm 3＋ cation is incorporated in the vacant site of the [ α-PW 11 O 39 H ] 6subunit and adopts square antiprismatic coordination geometry,while two adjacent monosubstituted anions [ α-PW 11 O 39 H ] 6are linked by two Sm-Ot-W bridges to form a dimer.