Polyoxometalate molecular science : proceedings of the NATO Advanced Study Institute, Tenerife, Spain, from 25 August to 4 September 2001

Polyoxometalates (POMs) form a large, distinctive class of molecular inorganic compounds of unrivaled electronic versatility and structural variation, with impacts ranging from chemistry, catalysis, and materials science to biology, and medicine. This book covers the basic principles governing the structure, bonding and reactivity of these metal-oxygen cluster anions and the major developments in their molecular science. The book comprises three sections. The first covers areas ranging from topological principles via synthesis and stability to reactivity in solution. It also focuses on the physical methods currently used to extract information on the molecular and electronic structures as well as the physical properties of these clusters. The second part reviews different types of POMs, focusing on those systems that currently impact other areas of interest, such as supramolecular chemistry, nanochemistry and molecular magnetism. The third section is devoted to POM-based materials and their applications and prospects in catalysis and materials science. Front Matter....Pages i-viii Front Matter....Pages 1-1 Introduction to Polyoxometalate Chemistry....Pages 3-31 General Principles of The Synthesis of Polyoxometalates in Aqueous Solution....Pages 33-54 General Strategies for Non-Aqueous Polyoxometalate Synthesis....Pages 55-78 Complex Oxides as Molecular Materials: Structure and Bonding in High-Valent Early Transition Metal Compounds....Pages 79-174 Physical Methods in Studying Polyoxometalates: Extended HÜCkel Molecular Orbital Calculations and Spectroscopic Properties....Pages 175-209 Time-Resolved Electron Spin Resonance Spectroscopy of Photoredox Reactions of Polyoxometalates: Formation of Paramagnetic-Species Pair by Triplet Mechanism....Pages 211-229 Front Matter....Pages 231-231 Functionalized Polyoxometalates....Pages 233-252 Sulfur-Containing Keggin Anions and Cyclic Polyoxothioanions....Pages 253-271 Magnetic Polyoxometalates....Pages 273-295 Combinatorially Linkable Metal-Oxide Based Units: Perspectives for Nano, Supramolecular, and Solid-State Chemistry....Pages 297-323 Front Matter....Pages 325-325 Applications of Polyoxometalates in Homogeneous Catalysis....Pages 327-349 Heterogeneous Catalysis by Heteropoly Compounds....Pages 351-380 Photochemistry and Photocatalysis by Polyoxometalates....Pages 381-416 Hybrid Materials Based on Polyoxometalates with Solid State Properties....Pages 417-440 Polyoxometalates in Tailored Supramolecular Architectures: From Structure to Function....Pages 441-466 Back Matter....Pages 467-474 Preface I: Basic Concepts and Principles.- Introduction to Polyoxometalate Chemistry.- General Principles of the Synthesis of Polyoxometalates in Aqueous Solution.- General Strategies for Non-Aqueous Polyoxometalate Synthesis.- Complex Oxides as Molecular Materials: Structure and Bonding in High-valent Early Transition Metal Compounds.- Physical Methods in Studying Polyoxometalates: Extended Hückel Molecular Orbital Calculations and Spectroscopic Properties.- Time-resolved Electron Spin Resonance Spectroscopy of Photoredox Reactions of Polyoxometalates: Formation of Paramagnetic Species Pair by Triplet Mechanism-.II: Relevant Types of POM Compounds. Functionalized Polyoxometalates.- Sulfur-containing Keggin Anions and Cyclic Polyoxothioanions.- Magnetic Polyoxometalates.- Combinatorially Linkable Metal-oxide Based Units: Perspectives for Nano, Supramolecular, and Solid-state Chemistry III: Materials and Applications. Applications of Polyoxometalates in Homogeneous Catalysis.- Heterogeneous Catalysis by Heteropoly Compounds.- Photochemistry and Photocatalysis by Polyoxometalates.- Hybrid Metals Based on Polyoxometalates with Solid State Properties.- Polyoxometalates in Tailored Supramolecular Architectures: from Structure to Function.- Index List of Contributors. The Keggin structure involves both edge- and corner-sharing of WQ¡ octahc-dra, and in 1937 Anderson proposed that the structures of the 6-heteropolyanions such as [IMO6O24]5- and the isopoly heptamolybdate anión were based entirely on edge-shared MoO6 octahedra [7].