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本文以砷钨多金属氧酸阴离子作为基本构筑模块,通过水热合成法制备了以饱和Keggin、饱和Dawson结构和单缺位、三缺位、四缺位Keggin结构多金属氧酸盐阴离子为构筑块的多系列多金属砷钨化合物,并对它们的组成、晶体结构、谱学性质(IR、ESR)、热性质(TG-DTA)、磁性质进行了表征和研究。(1)基于Keggin结构砷钨阴离子的有机/无机复合物: [Ni(phen)2][Hphen](AsW12O40),斜方晶系, P212121空间群, a = 12.2383(7), b = 21.0884(11), c = 22.3237(12),α=β=γ= 90°, Z = 4, R1 = 0.0376, wR2 = 0.0742;(2)基于Keggin结构阴离子的担载型砷钨化合物: [Fe(2,2′-bipy)3]1.5[AsWV2WVI12O40Fe(2,2′-bipy)2(H2O)]·0.25H2O,单斜晶系, C 1 2/c 1空间群, a = 46.8079(13), b = 14.3990(4), c = 26.1085(8)?,β= 90.00(5)°, Z = 8, R1 = 0.0484, wR2 = 0.1051;(3)基于单缺位Keggin结构阴离子的双系列砷钨化合物: [CuI(phen)2]5H6[Sm(AsW11O39)2]·6H2O,单斜晶系, P21/c空间群, a = 37.571(2), b = 13.9776(8), c = 33.3735(18)?,β= 96.9670(10)°, Z = 4, R1 = 0.0691, wR2 = 0.1525;(4)含RE/TM复合夹层的夹心型砷钨化合物: [Fe(phen)3]2[As2W18Fe2{Y(OH2)2}2O68]?6.5H2O,三斜晶系, Pī空间群, a = 12.8882(2), b = 13.4613(2), c = 17.7548(3)?,α= 95.0130(10),β= 104.1520(10),γ= 97.8220(10)°, Z = 1, R1 = 0.0473, wR2 = 0.1044;(5)担载型夹心结构砷钨化合物: [Ni(2,2′-bipy)3][As2W18Ni4(H2O)2{Ni(2,2′-bipy)2(H2O)}2{Ni(2,2′-bipy)}2O68]·4.5H2O,单斜晶系, C1 2/c 1空间群, a = 29.500(3), b = 24.804(2), c = 18.1476(16) ?,β= 94.34(0)°, Z = 4, R1= 0.0294, wR2 = 0.0660;(6)首例基于四缺位Keggin结构阴离子的二聚多金属砷钨酸盐: H2[{Cu(phen)}8(β-AsW8O31)2]·2.5H2O;单斜晶系, P21/c空间群, a = 21.346(6),b = 18.200(5), c = 18.482(5)?,β= 92.337(5)°, Z = 4, R1 = 0.0797, wR2 = 1697;(7)基于Dawson结构砷钨阴离子的有机/无机复合物: [Mn(2,2′-bipy)3]2[2,2′-Hbipy]2[As2W18O62],单斜晶系, P21/c空间群, a = 27.6608(12), b = 15.9390(7), c = 27.6608(12)?,β= 107.44°, Z = 4, R1 = 0.0531, wR2 = 0.1157;(8)包含一维金属氧簇阳离子的杂多化合物: [2,2′-H2bipy]2[{M(2,2′-bipy)}5O14]4(As2W18O62)2·8H2O (M = Mo, W),单斜晶系, C1 2/c 1空间群, a = 41.721(5), b = 24.629(5), c = 17.541(3)?,β= 91.12(0)°, Z = 2, R1 = 0.0672, wR2 = 0.1722;(9)基于饱和Dawson结构阴离子的二聚砷钨化合物: [Cu(2,2′-bipy)3]4H2[Cu(H2O)4(As2W18O62)2],三斜晶系, Pī空间群, a = 16.249(2), b = 16.735(2), c = 21.921(3)?,α= 93.885(3),β= 90.310(3),γ= 102.176(3)°, Z = 1, R1 = 0.0785, wR2 = 0.1692;(10)基于Dawson结构阴离子的一维链状砷钨化合物: H8[{CuI(en)2}4{CuI(H2O)(2,2′-bipy)}2{CuI(2,2′-bipy)(As2W17CuO61)}2]?4H2O;三斜晶系, Pī空间群, a = 11.640(3), b = 13.177(3), c = 31.143(7)?,α= 87.43,β= 84.47,γ= 68.02°, Z = 1, R1 = 0.0796, wR2 = 0.1728;(11)基于Dawson结构阴离子的二维层状砷钨化合物: [Cu(2,2′-bipy)3]2[Na4 (H2O)11(As2W18O62)]2?7H2O,六方晶系, P-6 2c空间群, a = 12.9175(7), b = 12.9175(7), c = 28.371(3)?,β= 120°, Z = 1, R1 = 0.0201, wR2 = 0.0501。