| Summary: | The organofunctionalisation of polyoxometalates (POMs) has emerged as a powerful strategy for enhancing the diversity of POM clusters, resulting in structures with tuneable electrochemical and photochemical properties. Despite notable progress, the integration of these functionalised POMs into organic photocatalysis remains limited. The work presented in this thesis aims to advance the scope of functionalised POMs beyond the current state-of-theart and to gain a greater understanding of how structural variations influence the photochemical properties of POMs.
Chapter 2 of this thesis focuses on the synthesis of organic-inorganic phosphotungstate hybrid Wells-Dawson POMs. This involves the study of their electro- and photochemical properties through voltametric and spectroscopic analysis. Discussions in this chapter will encompass the impact of structural variation, organofunctionalisation, and heteroanion modulation, on the estimated frontier orbital energies of the POMs. Chapter 3 extends this study by detailing the synthesis and structural elucidation of novel borotungstate Keggin hybrids. This exploration delves into the distinctive characteristics of this family of POMs, contributing to the broader understanding of the impact of structural variation on their properties of hybrid POMs. The concluding chapter focuses the application of organo-functionalised hybrid POMs, with particular focus on borotungstate hybrids, as photocatalysts in organic synthesis. Specifically, their role as single electron transfer (SET) catalysts will be investigated, with application to the photooxidative coupling of amines.
In summary, this comprehensive study hopes to not only advance the current understanding of the intricate relationships between structural modifications of organofunctionalised hybrid POMs and their tuneable electro- and photochemical properties, but to also gain insight into their potential applicability in organic photocatalysis.
|
|---|