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本文基于分子设计及组装的思想,采用水热合成法或常温合成制备了以B-[SbW9O33]9-或其衍生的构筑单元的多金属氧簇,并对它们的晶体结构、谱学性质、热性质、电化学性质以及磁性质进行了研究。(I)合成了一个新颖的基于[B-α-SbW9O33]9-构筑单元的有机-无机配位聚合物Na[{Cu(2,2′-bpy)(H2O)}2{Cu(2,2′-bpy)}2(B-α-SbW9O33)]·2H2O (1),化合物在Na+离子的作用下连接形成了一维链。(II)得到两个以类Dawson结构多阴离子{SbW18O60}为基本构筑块,以2,2′-bipyridine为有机配体的有机-无机杂化的多金属氧酸化合物:[Co(2,2′-bpy)3]2[Co(2,2′-bpy)2Cl][Co(2,2′-bpy)2]H2[SbW18O60]·4H2O (2)和[Cu(2,2′-bpy)3]2[Cu(2,2′-bpy)2Cl][Cu(2,2′-bpy)2]H6[SbWV4WVI14O60]·H2O (3)。(III)合成三个对称的夹心型配合物Na8K[Na2K(H2O)2{Co(H2O)}3(B-α- SbW9O33)2]·10H2O (4)、K4Na2H3[Na2K(H2O)2{Cu(H2O)}3(α-SbW9O33)2]·15H2O (5)和NaH8[Na2Cu4Cl(B-α-SbW9O33)2]·21H2O (6),这些化合物是基于[B-α-SbW9O33]9-构筑单元的对称的夹心化合物,其中化合物6以铜离子为桥形成了二维层状结构。(IV)合成两个错位的夹心型配合物Na5H[{Co(H2O)2}3W(H2O)2(B-β- SbW9O33)2]·11.5H2O (7)和Na4H4[{Ni(H2O)3}2{W(OH)2}2{B-β-SbW9O33}2]·23H2O (8),这些化合物是基于[B-β-SbW9O33]9-构筑单元的错位的夹心结构;其中化合物7以钴和钠离子为桥形成了三维网状结构。以上化合物分别用元素分析、IR、XPS、EPR、TGA、CV、磁性和单晶X-射线衍射等方法进行了表征和性质研究。化合物的组成和主要晶体学数据如下:1. Na[{Cu(2,2′-bpy)(H2O)}2{Cu(2,2′-bpy)}2(B-α-SbW9O33)]?2H2O (1):尺寸0.13×0.11×0.10 mm,晶体属正交晶系, Pnma空间群,晶胞参数: a = 17.174(2) ?, b = 24.572(4) ?, c = 15.267(2) ?, V = 6442.3(16) ?3, Z = 4,μ= 17.801 mm–1, Dc = 3.375 Mg/m3, T = 293(2) K, 2.44 <θ< 25.00o,结构参数487个,最终偏移因子R1 = 0.0401, wR2 = 0.1079.2. [Co(2,2′-bpy)3]2[Co(2,2′-bpy)2Cl][Co(2,2′-bpy)2]H2[SbW18O60]?4H2O (2):尺寸0.16×0.13×0.12 mm,晶体属正交晶系, Pba2空间群,晶胞参数: a = 21.208(2) ?, b = 24.506(2) (4) ?, c = 12.931(1) ?, V = 6720.7(9) ?3,μ= 6.124 mm–1, Dc = 3.107 Mg/m3, Z = 2, T = 293(2) K, 2.02 <θ< 25.00o,结构参数957个,最终偏移因子R1 = 0.0416, wR2 = 0.0771.3. [Cu(2,2′-bpy)3]2[Cu(2,2′-bpy)2Cl][Cu(2,2′-bpy)2]H6[SbWV4WVI14O60]?H2O (3):尺寸0.16×0.13×0.11 mm3,晶体属正交晶系, Pba2空间群,晶胞参数: a = 21.207(3) ?, b = 24.466(4) ?, c = 12.992(2) ?, V = 6740.9(17) ?3,μ= 16.211 mm–1, Dc = 3.084 Mg/m3, Z = 2, T = 293(2) K, 2.48 <θ< 25.00o,结构参数935个,最终偏移因子R1 = 0.0464, wR2 = 0.1232.4. Na8K[Na2K(H2O)2{Co(H2O)}3(B-α-SbW9O33)2]?10H2O (4):尺寸0.15×0.13×0.12 mm3,晶体属正交晶系, Pnma空间群.晶胞参数: a = 30.579(10) ?, b = 15.073(5) ?, c = 19.180(6) ?, Z = 4, V = 8840(5) ?3,μ= 24.704 mm–1, Dc = 4.030 Mg/m3, T = 293(2) K, 2.12 <θ< 25.00o,结构参数559个,最终偏移因子R1 = 0.0536, wR2 = 0.1267.5. K4Na2H3[Na2K(H2O)2{Cu(H2O)}3(α-SbW9O33)2]?15H2O (5):尺寸0.14×0.10×0.08 mm3,晶体属正交晶系, Pnma空间群.晶胞参数: a = 30.2536(13) ?, b = 15.0639(7) ?, c = 19.1203(8) ?, V = 8713.8(7) ?3,μ= 225.344 mm–1, Dc = 4.154 Mg/m3, Z = 4, T = 293(2) K, 1.72 <θ< 25.00o,结构参数601个,最终偏移因子R1 = 0.0755, wR2 = 0.1953.6. NaH8[Na2Cu4Cl(B-α-SbW9O33)2]?21H2O (6):尺寸0.13×0.11×0.10 mm3,晶体属正交晶系, P421m空间群.晶胞参数: a = 16.834(2) ?, b = 16.834(2) ?, c =13.729(3) ?,V = 3890.5(11) ?3,μ= 28.410 mm–1, Dc = 4.570 Mg/m3, Z = 2, T = 293(2) K, 2.5 <θ< 25.00o,结构参数288个,最终偏移因子R1 = 0.0454, wR2 = 0.1032.7. Na5H[{Co(H2O)2}3W(H2O)2(B-β-SbW9O33)2]?11.5H2O (7):尺寸0.16×0.13×0.11 mm3,晶体属三斜晶系, Pī空间群.晶胞参数: a = 12.0974(14) ?, b = 17.869(2) ?, c = 20.323(2) ?,α= 92.6870(10)°,β= 91.444(2)°,γ= 107.111(2)°, V = 4190.6(8) ?3,μ= 27.302 mm–1, Dc = 4.309 Mg/m3, Z = 2, T = 293(2) K, 2.5 <θ< 25.00o,结构参数1108个,最终偏移因子R1 = 0.0592, wR2 = 0.1442.8. Na4H4[{Ni(H2O)3}2{W(OH)2}2{B-β-SbW9O33}2]?23H2O (8):尺寸0.14×0.12×0.11 mm3,晶体属单斜晶系, P21/n空间群.晶胞参数: a = 12.890(5) ?, b = 25.046(9) ?, c = 15.978(6) ?,β= 94.491(5)°, V = 5142(3) ?3,μ= 23.262 mm–1, Dc = 3.733 Mg/m3, Z = 2, T = 293(2) K, 2.5 <θ< 25.00o,结构参数604个,最终偏移因子R1 = 0.0709, wR2 = 0.1955.