Group IV metal clusters as discrete building blocks for the synthesis of metal-organic frameworks

Ollier de Marichard, Alexandre (2022) Group IV metal clusters as discrete building blocks for the synthesis of metal-organic frameworks. MRes thesis, University of Nottingham.

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Abstract

This thesis shows my investigations into the formation of metal-organic frameworks from discrete group IV metal clusters. To that end, three clusters were synthesised, namely Zr6 benzoate, Zr6 methacrylate and Ti6 aminobenzoate. Novel clusters were synthesised, but poor crystallinity meant that they could not be fully characterised, and therefore were not suitable for further reactions.

Using these three clusters, MOFs were synthesised. In typical MOF reactions starting from a metal salt and a linker, metal-oxo clusters are formed through self-assembly. Starting from pre-synthesised clusters has the potential to lead to milder synthetic conditions, and offer control over the nature and topology of the framework. The conditions needed for the formation of crystalline MOFs from clusters were investigated through systematic modifications of the reaction conditions. Changes in reaction temperatures and times, molar ratios and concentrations led to little change in the crystallinity of the obtained products. Modulation led to a significant change in crystallinity and particle sizes. This suggested that the modulation mechanism in MOFs is more complex than the common understanding, and that “self-modulating” properties of discrete clusters were not the main mechanism. It was also established that modulation is dependent on the clusters’ metal and associated ligand.

Finally, using a mixture of two different metal clusters, the synthesis of mixed-cluster MOFs was attempted. While these attempts did not produce the desired products, it helped to emphasize the issues associated with them, as well as the possible conditions needed for successful synthesis.

Item Type: Thesis (University of Nottingham only) (MRes)
Supervisors: Cliffe, Matthew
Keywords: Group IV metal clusters, Metal-organic frameworks
Subjects: Q Science > QD Chemistry > QD241 Organic chemistry
Faculties/Schools: UK Campuses > Faculty of Science > School of Chemistry
Item ID: 68926
Depositing User: Ollier de Marichard, Alexandre
Date Deposited: 02 Aug 2022 04:40
Last Modified: 02 Aug 2022 04:40
URI: http://eprints.nottingham.ac.uk/id/eprint/68926

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