Asymmetric Amine-Carboxylic Acid Organic Inorganic Hybrid Wells Dawson Polyoxometalates

Abstract

Symmetric organofunctionalised polyoxometalates have been widely studied in recent years, due to their desirable characteristics, including catalytic properties and varied redox behaviour. However, limited research has been conducted into the design, synthesis and characterisation of asymmetric organofunctionalised hybrid POMs. These are of increasing interest because of their tunable electronic properties and ability to access precise functionality. This work discusses the process of successful synthesis and characterisation of symmetric hybrid Polyoxometalates [P2W17O57{(PPA)2}] and [P2W17O57{(AEP)2}] and designing accessible synthetic processes for creating multifunctional hybrid materials that provide good control in modifying their structure and characteristics is a persistent issue. The availability of asymmetrically organofunctionalised hybrid polyoxometalates (POMs) offers the potential for developing new molecular materials with various functions that can be adapted to meet the needs of specialised applications. A simple, low-cost, and high-yielding one-pot synthesis technique based on the Wells–Dawson anion was attempted to be employed in the process of isolating a novel asymmetric hybrid POM [P2W17O57{(PPA) (AEP)}]. This thesis discusses the development of the synthetic method as well as the characterisation of the asymmetric bi-functionalised hybrid polyoxometalates structure that the hybrid molecule has. The inclusion of transition metal functionality into the asymmetric hybrid POM at the attached chelating group is investigated, and synthetic strategies are described. As an organophosphonate ligand, a ruthenium(II) polypyridyl complex is produced for direct grafting to the cluster anion during a modified one-pot synthesis.