介绍了近几年来多金属氧酸盐(polyoxometalate,缩写为POM)在合成化学研究方面的新进展,内容包括:由水热合成方法得到的Keggin型[SiNb12 O40]^16-及其与[Ti2O2]^4+连接构成的一维链状结构及[H2Si4Nb15O56]^14-簇;Silverton型多阴离子[GdMo12O40]^9-及三维网络结构;POM和过渡金属簇通过有机π共轭体系形成的杂化材料;一步法自组装合成的四核轮状的多金属钨酸盐;控制合成得到具有蛋白质尺寸的Mo368氧簇和开普勒环形山结构的多钼氧簇;用{P2W12}杂多阴离子作为建筑块合成出的含有20个Cu中心的大轮型POM;用常规方法突破“氧墙”效应,获锝的第一例稳定的含有第三过渡金属元素的多金属氧酸盐;通过逐步合成法用[SiW9O34]^10-作为建筑单元合成出二聚和四聚的POM化合物;合成带有均匀孔道结构,具有选择性吸附和分离混合低碳脂肪醇和低碳氰分子的三维网络结构等.
This paper reviews new developments of the synthesis chemistry of polyoxometalates (POM). Its content includes: heteropolyniobates, K12 [Ti2 O2 ] [SiNb12 O40 ] · 16 H2 O, which contains 1D chains constructed by [Ti2O2]^4+ and [SiNb12O40]^16- ,and a new POM [H2Si4Nb16O56]^14-obtainted by hydrothermal synthesis method,and Silverton type [GdMol2O40 ]^9- polyanion and a novel 3D framework. The first hybrid in which a POM cluster and transition-metal complexes are linked through an extended π-conjugated bridge. A unique tetrameric and cyclic tungstosilicate has been synthesized by using mild "one-pot" reaction method. A large, wheel-shaped, Cu20 containing polyanion by direct reaction of Copper( Ⅱ ) ions with [ H7 P8 W48 O184 ]^33-. Hill presented a route to break through the "oxo wall" and stabilize a single (H2O)Pt=O moiety by using electron-withdrawing {PW9 } building blocks as ligands to sandwich the Pt=O moiety. The resulting complex is the first discrete metal oxo complex of a late transition metal. Condensation of [SiW9 O34]^10- anions in successive steps gives dimeric and tetrameric species. The giant wheels (molybdenum blue), the {Mo368 } nanohedgehog, and nanosized porous spherical clusters (keplerates) were reporred by Mueller.