Polyoxometalate Chemistry: An Old Field with New Dimensions in Several Disciplines

作者：Michael T. Pope, Achim Müller · 发表于：Angewandte Chemie International Edition in English · 年份：1991 · DOI：10.1002/anie.199100341 · 被引用次数：3610 · 研究领域：Polyoxometalates: Synthesis and Applications、Metal-Organic Frameworks: Synthesis and Applications、Vanadium and Halogenation Chemistry

Abstract Inorganic metal–oxygen cluster anions form a class of compounds that is unique in its topological and electronic versatility and is important in several disciplines. Names such as Berzelius , Werner , and Pauling appear in the early literature of the field. These clusters (so‐called isopoly‐ and heteropolyanions) contain highly symmetrical core assemblies of MO x units (M = V, Mo, W) and often adopt quasi‐spherical structures based on Archimedean and Platonic solids of considerable topological interest. Understanding the driving force for the formation of high‐nuclearity clusters is still a formidable challenge. Polyoxoanions are important models for elucidating the biological and catalytic action of metal–chalcogenide clusters, since metal–metal interactions in the oxo clusters range from very weak (virtually none) to strong (metal–metal bonding) and can be controlled by choice of metal (3d, 4d, 5d), electron population (degree of reduction), and extent of protonation. Mixed‐valence vanadates, in particular, show novel capacities for unpaired electrons, and the magnetic properties of these complexes may be tuned in a stepwise manner. Many vanadates also act as cryptands and clathrate hosts not only for neutral molecules and cations but also for anions, whereby a remarkable “induced self‐assembly process” often occurs. Polyoxometalates have found applications in analytical and clinical chemistry, catalysis (including photocatalysis), biochemistry (electron transport ...