Latest progress in asymmetrically functionalized Anderson-type polyoxometalates

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Abstract

Asymmetrically functionalized Anderson-type polyoxometalates were overviewed, including the key factors of various synthesis methods, separation methods, advantages of asymmetric structures, and their applications.

Abstract

Anderson-type polyoxometalates (POMs) are one of the most important and widely developed groups of the POM family. The covalent functionalization of Anderson POMs has attracted extensive attention and facilitated broad applications of the resultant POM hybrids in catalysis, biology, energy materials and medicine. Among the various synthetic methods for Anderson hybrids, asymmetric functionalization has been one of the hottest and unique topics in the last decade. In the structure of asymmetric Anderson hybrids, two different organic components are anchored onto each side of the Anderson cluster or only one side of the cluster is functionalized. Asymmetric functionalization provides complexity to POM assemblies and merges multiple functions into one hybrid molecule, meanwhile, bringing challenges of rational design and controllable synthetic strategies. In this review, the latest progress in the synthetic methods and applications of asymmetrically functionalized Anderson-type POMs is summarized according to the central heteroatom of the cluster, which includes Mn-, Cr-, Al- and other metal-templated Anderson POMs.

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Hybrid organic-inorganic polyoxometalate compounds: from structural diversity to applications.

Anne Dolbecq, Eddy Dumas, Cédric R. Mayer … (2010)

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Functionalization of polyoxometalates: towards advanced applications in catalysis and materials science.

Anna Proust, René Thouvenot, Pierre Gouzerh (2008)

Functionalization via covalent grafting of organic functions allows to tune the redox and acid-base properties, and the solubility of polyoxometalates, to enhance their stability and biological activity and to reduce their toxicity, to facilitate their implementation in extended structures and functional devices. We discuss herein the electronic and binding connections, and the various synthesis methodologies. We emphasize on organonitrogen, organosilyl and organophosphonyl derivatives with special attention to synthesis, characterization and potential applications in catalysis and materials science. We also consider the giant molybdenum oxide-based clusters especially the porous capsule-type clusters (Keplerates) which have high relevance to this context.

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Engineering polyoxometalates with emergent properties.

Haralampos Miras, Jun Yan, De-Liang Long … (2012)

Polyoxometalates are clusters of metal-oxide units, comprising a large diversity of nanoscale structures, and have many common building blocks; in fact polyoxometalate clusters are perhaps the largest non-biologically derived molecules structurally characterised. Not only can polyoxometalates have gigantic nanoscale molecular structures, but they also a have a vast array of physical properties, many of which can be specifically 'engineered-in'. Here we describe how building block libraries of polyoxometalates can be used to construct systems with important catalytic, electronic, and structural properties. We also show that it is possible to construct complex chemical systems based upon polyoxometalates, manipulating the templating/self templating rules to exhibit emergent processes from the molecular to the macroscopic scale.