Supramolecular assemblies in solid-state, solution and gas-phase

The first part of the work presented within this thesis focuses on the electrochemical properties of supramolecular heteropolyoxotungstate frameworks substituted with cobalt or manganese and the synthesis of molecular alloys containing intrinsic mixtures of these two late transition metals. The single crystal to single crystal transformations that these compounds undergo upon redox reactions are presented and the impact on the redox kinetics that the heteroatom, silicon or germanium, in the polyoxometalate (POM) clusters centres exhibits is investigated. Furthermore, a synthetic approach for the formation of molecular alloy materials where cobalt and manganese are intrinsically mixed in the framework was developed. These alloys possess novel properties when compared to those of the native compounds, where only one of the two late transition metals is incorporated. The second part of this thesis introduces ion-mobility mass spectrometry (IMS-MS) as a new tool in the analysis and characterisation of metal oxides and demonstrates potential applications of this technique using several examples of POM clusters. The formation of supramolecular assemblies of organically functionalised POMs is revealed and the influence on the assemblies’ sizes for a range of different organic ligands is investigated. Additionally, IMS-MS is demonstrated as a useful tool to distinguish between two isomers of POMs functionalised with photo-switchable organic ligands. The fragmentation and supramolecular assemblies of a dimeric polyoxovanadate cluster are examined and several classic phosphotungstate clusters are analysed by the use of IMS-MS