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Alkoxido-Derivatised Lindqvist and Keggin Type Polyoxometalates

Lookup NU author(s): Dr John ErringtonORCiD, Balamurugan Kandasamy, Daniel Lebbie, Thompson Izuagie

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Abstract

The targeted application of polyoxometalates (POMs) in catalysis, materials science and biology requires an in depth understanding of how their properties might be tuned through compositional and structural molecular engineering. In practice, this requires chemical methodologies that enable reliable, systematic manipulation of families of related POMs in conjunction with detailed experimental and theoretical studies. Lindqvist-type hexametalates [LM′M₅O₁₈]^n– provide a convenient platform for systematic studies in which M, M′ and L may be varied, and this chapter gives an overview of the development of versatile synthetic methods and the results of detailed reactivity studies based on alkoxido-derivatised anions [(RO)M′M₅O₁₈]^n–. Solid state structures and NMR studies of solution reactivities are providing an insight into the effects on bonding and electronic properties of metal and ligand substitution in this family of POMs, and comparisons with the related Keggin-type POMs [(RO)M′PW₁₁O₃₉] enable an assessment of the effect of the supporting POM structure on the reactivity of the heterometal site. The chapter begins with recent investigations of aggregation in non-aqueous synthesis of POMs from metal alkoxides and the introduction of heterometal sites into the hexametalate framework. Subsequent sections discuss how protonolysis of M′OR bonds can be used in synthesis of ligand-exchanged anions and also for the generation of highly reactive {M′M₅} species in solution

Publication metadata

Author(s): Errington RJ, Kandasamy B, Lebbie D, Izuagie T

Editor(s): Song, Y-F

Series Editor(s): Mingos, DMP

Publication type: Book Chapter

Publication status: Published

Book Title: Polyoxometalate-Based Assemblies and Functional Materials

Year: 2017

Pages: 1-25

Online publication date: 13/10/2017

Acceptance date: 14/09/2017

Series Title: Structure and Bonding

Publisher: Springer

URL: https://doi.org/10.1007/430_2017_10

DOI: 10.1007/430_2017_10

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