Insights into Self-Assembly, Proton-Transfer and Reduction in Non-Aqueous Polyoxometalate Chemistry

Interest in polyoxometalates has expanded in recent years with the growing awareness of their remarkably versatile properties and the wide variety of potential applications. This talk will describe our efforts to develop new and rational reactivity together with a deeper understanding of fundamental polyoxometalate solution chemistry. Non-aqueous methodologies facilitate the synthesis of a range of heterometal-substituted Lindqvist and Keggin type POMs and extensive ¹⁷O NMR studies. Mechanistic aspects of hydrolytic assembly, protonolysis and protonation will be discussed, including theoretical analysis of variations arising from structural and compositional differences. Non-aqueous reactions aimed towards super-reduced derivatives and the resulting series of electron-rich POMs will be described, highlighting the relevance to electron-storage applications.