Catalysis of Photochemical Reactions Using Soft-Oxometalates and Supramolecular Assemblies

Das, Kousik (2020) Catalysis of Photochemical Reactions Using Soft-Oxometalates and Supramolecular Assemblies. PhD thesis, Indian Institute of Science Education and Research Kolkata.

Text (Phd thesis of Kousik Das (13RS035)) 13RS035.pdf - Submitted Version Restricted to Repository staff only Download (7MB)

Abstract

In this dissertation, we have demonstrated the importance of supramolecular interactions in catalysis in the context of oxometalates and thio-metalates and in their soft-matter states. Several non-bonding interactions come into play during the formation of a supramolecular assembly. We take advantage of these weak supramolecular forces for substrate recognition, binding and activation. Oxometalates and their hybrids form such supramolecular entities due to the counterion mediated attraction. Through the engineering of counterions, we were able to synthesize a variety of supramolecular structures based on oxometalates which we call as ‘soft-oxometalates’ (SOMs). Moreover such control over their synthesis led us to perform catalysis in ultra-violet light as well as in visible light. In addition to that, the structures are endowed with excellent redox property and stability due to the inherent properties of the building oxometalate units. Combining these features we were able to perform series of catalytic reactions starting from polymerization, organic oxidation to conversion of CO₂ to produce chemical fuels. We were also able to monitor the reaction rate and product selectivity due to the enhanced interaction in the compartmentalized space provided by these supramolecular structures.

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