Synthesis of sulfur and selenium doped anthanthrene and PXX catalysed photoredox aryl coupling reactions

Matuszewska, Oliwia 2021. Synthesis of sulfur and selenium doped anthanthrene and PXX catalysed photoredox aryl coupling reactions. PhD Thesis, Cardiff University. Item availability restricted.

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Abstract

Polycyclic aromatic hydrocarbons (PAHs) have been widely studied, as they have found multiple applications in the field of organic electronics. Among various methods of influencing the properties of PAHs, doping with heteroatoms was found to be a versatile strategy. One such PAH is peri-xanthenoxanthne (PXX), which is an O doped anthanthrene investigated as an organic semiconductor by SONY. The first part of this thesis focuses on the synthesis of sulfur- (PTXTX) and selenium�doped PXX derivatives. PTXTX and a range of its derivatives with solubilising groups and different oxidation levels have been synthesised. It has been also shown that electrophilic aromatic substitution can be utilised towards the synthesis of Se doped PAHs. The X-ray crystal structures and optoelectronic properties of synthetised compounds have been investigated. The applications of PTXTX in multivalence complexes and LEC devices have been shortly described. In the second project, our goal was to utilise PXX as a photoredox catalyst. PXX is strongly reducing in the singlet excited state, metal-free and easy to synthesise, making it a potentially useful chromophore. PXX was able to photoredox catalyse intermolecular coupling of electron-poor aryl halides with electron-rich radical traps. Additionally, a novel cyclisation reaction of aryl chlorides, leading to the synthesis of PAHs has been shown. Under blue light irradiation, PXX catalysed intramolecular coupling of o-terphenyl chlorides possessing electron-withdrawing group (EWG) on the ring with a chlorine atom. A range of mono and disubstituted triphenylenes was achieved in good yields. Products with different substituents, such as EWGs and electron-donating groups (EDGs) as well as structures with heteroarenes were successfully obtained. A double cyclisation led to an unexpected disubstituted tetraphenylene derivative, achieving a new route towards this important class of compounds

Item Type:	Thesis (PhD)
Date Type:	Completion
Status:	Unpublished
Schools:	Chemistry
Funders:	European Union’s Horizon 2020 Research and Innovation Program under the Marie Sklodowska-Curie Actions H2020-MSCA-ITN-2016-722591 (PHOTOTRAIN)
Date of First Compliant Deposit:	30 May 2023
Last Modified:	30 May 2024 01:30
URI:	https://orca.cardiff.ac.uk/id/eprint/160029

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