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本文以Dawson结构和Anderson结构聚金属氧酸阴离子出发,通过向分子内引入金属离子,采用常温水溶液(或混合溶剂)及水浴回流等合成方法,合成出不同类型的聚金属氧酸稀土、碱土配位聚合物,并对它们的晶体结构、谱学性质、热性质、电化学性质等进行了研究。(1)常温下合成了两个新型三维网状Dawson结构聚金属氧酸阴离子碱土金属衍生物H2[Ca2(P2W18O62)(H2O)5]7.5H2O(1)和H2[Ca2(P2W18O62)(H2O)5]·9H2O(2),并对其进行了结构和谱学表征,研究了它们的电化学性质,结构分析表明两个化合物均通过碱土金属Ca2+相连形成三维网状结构。(2)从饱和Dawson结构磷钨酸盐出发,常温下合成了单缺位Dawson结构阴离子稀土衍生物的二聚化合物Na14[{Nd(H2O)3(α2-P2W17O61)}2]·17H2O(3),经IR和X-射线单晶衍射等手段进行了表征,并对其热性质及电化学性质进行了研究。(3)常温下合成了Anderson结构聚金属氧酸阴离子一维锯齿链状稀土衍生物[Nd(H2O)7][Cr(OH)6Mo6O18]·4H2O(4),测定了其结构,并用元素分析,IR,TG等手段对化合物进行了表征和性质研究。化合物的组成和晶体数据如下:1. H2[Ca2(P2W18O62)(H2O)5]·7.5H2O:晶体属三斜晶系, Pī空间群.晶胞参数: a = 12.933(5) A, b = 14.878(6) A, c = 20.048(8) A,α= 70.253(5)o,β= 80.800 (5) o,γ=64.425(4)o, V=3275(2) A3, Dc =4.737Mg/m3, Z = 2, GOF = 0.943, F(000) = 4050, R1 = 0.0732, wR2 = 0.1881, Rint = 0.1097.2.H2[Ca2(P2W18O62)(H2O)5]·9H2O:晶体属三斜晶系, Pī空间群.晶胞参数: a = 12.9077(14) A, b = 14.8593(16) A, c = 20.023(2) A,α= 70.1620(10)o,β= 80.8110 (10)°,γ= 64.3770(10)o, V = 3256.9(6) A3, Dc = 4.790Mg/m3, Z = 2, GOF = 1.023, F(000) = 4080, R1 = 0.0412, wR2 =.0.1074, Rint= 0.0413.3.Na14[{Nd(H2O)3(α2-P2W17O61)}2]·17H2O:晶体属三斜晶系, Pī空间群.晶胞参数: a = 12.6738(15) A, b = 14.1464(17) A, c = 23.254(4) A,α= 103.142(2)o,β= 95.122(2)°,γ= 113.9690(10)o, V =3631.7(8) A3, Dc = 4.274 Mg/m3, Z = 2, GOF=0.984, F(000) = 4052, R1 = 0.0491, wR2=.0.1401, Rint=0.0563.4.[Nd(H2O)7][Cr(OH)6Mo6O18]·4H2O:晶体属正交晶系,pca21空间群.晶胞参数: a =11.8655(10) A, b =10.9961(9) A, c = 22.5449(18) A,α= 90o,β= 90 o,γ= 90o, V = 2941.5(4)A3, Dc = 3.071 Mg/m3, Z = 4, GOF =1.063, F(000) = 2576. R1= 0.0241, wR2=0.0624, Rint= 0.0210.