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Walters, Kai (2022) The synthesis and properties of organic-inorganic hybrid polyoxometalates hybridised with asymmetric perylenediimides. MRes thesis, University of Nottingham.

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Abstract

In recent years there has been a growing interest in producing sustainable and efficient catalysts. Within this area of research there has been a focus in harnessing solar energy to drive reactions. Polyoxometalates (POMs) have attracted substantial attention in the field of photocatalysis due to their vast structural diversity, inherent redox activity, and photochemical properties. Despite the promising chemical profile of POMs and their potential in photocatalysis, they have been limited by their absorption characteristics which lie almost exclusively within the UV range and show little to no absorption in the visible light region.

Developments in POM chemistry have allowed for new functionalisation strategies to tune the optical, electrochemical and solubility of POM photocatalysts. There has been a growing interest in hybridisation of POMs with photoactive species (chromophores) with the goal of sensitising the POM to visible light and enhance catalytic capacity through intermolecular charge transfer. Perylene diimides (PDIs) have been of particular interest for this purpose due to their excellent absorption and emission profiles and photochemical stability. Asymmetric synthesis approaches have allowed further tweaking of the optical and electronic properties of PDIs and are potentially attractive to complement the properties of POMs forming new visible light driven photocatalysts.

This report describes the synthesis and characterisation of a novel hybrid organic-inorganic POM. Careful consideration has been made into the molecular design of an asymmetric PDI that will impart the best physical and chemical properties to the photocatalytic dyad. The [P2W17O61(C39H33N2O5P)2] anion was successfully synthesized and characterized by complimentary NMR, mass spectrometry, TGA, IR, UV-vis, fluorescence spectroscopy and electrochemistry. The hybrid POM was successfully synthesised and evidence for favourable intermolecular charge transfer between the PDI and POM components was observed.

Item Type:	Thesis (University of Nottingham only) (MRes)
Supervisors:	Newton, Graham
Keywords:	Asymmetric perylenediimides, Polyoxometalates
Subjects:	Q Science > QD Chemistry > QD146 Inorganic chemistry
Faculties/Schools:	UK Campuses > Faculty of Science > School of Chemistry
Item ID:	68543
Depositing User:	Walters, Kai
Date Deposited:	02 Aug 2022 04:40
Last Modified:	02 Aug 2022 04:40
URI:	https://eprints.nottingham.ac.uk/id/eprint/68543

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