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本文基于分子设计及组装的思想,通过水热合成法制备了以Keggin结构[BW12O40]5–多金属氧酸阴离子等为构筑块的一系列多金属氧酸衍生物,并对它们的晶体结构、谱学性质(IR、XPS)、热性质(TG)进行了表征和研究。I.合成了两个基于Keggin结构硼钨酸阴离子的有机/无机复合物:1. [Mn(phen)3]2H[BW12O40]A3H2O:尺寸0.12×0.10×0.09 mm,单斜晶系,C2/c空间群,a = 27.285(3)A, b = 25.060(3)A, c = 16.336(18) A,β= 104.911(2)°, V = 10794(2)A3, Z = 4, R1 =0.0784, wR2 = 0.1999.2. [Cu(en)2(H2O)][Cu(en)2]2H3[BW11.75Cu0.25O40]·3.75H2O:尺寸0.12×0.10×0.09 mm,正交晶系,Pbca空间群,a = 21.5438(18)A, b = 20.6591(18)A, c = 26.052(2)A,β= 90.00°, V = 11595.2(17)A3, Z = 8, R1 = 0.0306, wR2 = 0.0666.II.基于Keggin结构阴离子的担载型多金属氧酸化合物:3. [Mn(2,2’-bipy)3]1.5[BW12O40Mn(2,2’-bipy)2(H2O)]A0.25H2O:尺寸0.12×0.10×0.08,单斜晶系,C2/c空间群,a = 46.812(16)A, b = 14.447(5)A, c = 26.083(9)A,β= 90°, V = 17639(11)A3, Z = 8, R1 = 0.0561, wR2 = 0.1451.4. [Fe(2,2’-bipy)3]1.5[BW12O40Fe(2,2’-bipy)2(H2O)]A0.5H2O:尺寸0.14×0.12×0.11,单斜晶系,C2/c空间群,a = 46.633(5)A, b = 14.3156(16)A, c = 25.976(3)A,β= 90°, V = 17341(3)A3, Z = 8, R1 = 0.0457, wR2 = 0.0771.5. [Cu2(phen)2(OH)2]2H[Cu(H2O)2{BW12O40Cu0.75(phen)(H2O)}2]A1.5H2O:尺寸0.15×0.13×0.11,单斜晶系,C2/c空间群,a = 43.888(9)A, b = 23.966(5)A, c = 13.744(3) A,β= 102.77(3)°, V = 14099(5)A3, Z = 4, R1 = 0.0695, wR2 = 0.1111.6. [Co(2,2′-bipy)3]1.5[SiWVWVI11O40Co(2,2′-bipy)2(H2O)]·0.5H2O:尺寸0.12×0.10×0.09,单斜晶系,C2/c空间群,a = 46.995(15)A, b = 14.487(5)A, c = 26.205(9)A,β= 90.000(0)°, V = 17841(10)A3, Z = 4, R1 = 0.0660, wR2 = 0.0660.III.基于单缺位Keggin结构阴离子的稀土衍生物:7. [Cu(en)2]2H8[Gd(PW11O39)2]A(H2en)0.5A3H2O:尺寸0.11×0.11×0.10,三斜晶系,P-1空间群,a = 12.651(2) A, b = 20.559(3) A, c = 21.729(3) A,α= 71.379(2),β= 82.829(2),γ= 75.532(2)°, V = 5179.5(14)A3, Z = 2, R1 = 0.0702, wR2 = 0.1479.IV.β-八钼酸阴离子支撑的多金属氧酸盐化合物:8. H4{[Cu2(ophen)2]2[Mo8O26]}[Cu2(ophen)2]·H2O:尺寸0.16×0.14×0.13,三斜晶系,P-1空间群,a = 9.9091(8) A, b = 13.3981(8) A, c = 14.8266(10) A,α= 84.6310(10),β= 83.0620(10)°,γ= 77.7800(10), V = 1905.0(2)A3, Z = 1, R1 = 0.0269, wR2 = 0.0669.