Photoinduced Electron Transfer in Triangulenium Fluorophores: The Application of Intra- and Intermolecular Electron Transfer

Publikation: Bog/antologi/afhandling/rapportPh.d.-afhandlingForskning

Abstract

This thesis describes the synthesis and characterization of a range of triangulenium fluorophores with the goal of studying and applying intra- and intermolecular photoinduced electron transfer (PET).

Chapter 1 provides an introduction to molecular fluorophores, and the applications of PET as an analytical tool and in relation to photoredox catalysis. Chapter 2 deals with the synthesis and photophysical characterization of new hydroxybenzoic acid substituted diazaoxatriangulenium (DAOTA+) fluorophores. The fluorophores were used to study proton transfer mechanisms in water, and the results support the Grotthuss mechanism. In Chapter 3 the triangulenium fluorophores azadioxatriangulenium (ADOTA+), DAOTA+, and triazatriangulenium (TATA+) were applied as photoredox catalysts. Showcasing how the electronic structure of the fluorophores controls the excited state redox properties, and thereby the photoredox catalytic reactivity. TATA+ is the most electron rich triangulenium, and the best excited state electron donor, while ADOTA+ is the least electron rich triangulenium, and the best excited state electron acceptor. Chapter 4 introduces the synthesis of a novel family of fluorescent acridiniums, and their application as excited state electron acceptors in photoredox catalysis. The fluorescent properties are enabled because of the inhibition of intramolecular PET quenching. This was realized by functionalization with electron withdrawing groups through electrophilic aromatic substitution reactions. Finally, Chapter 5 reports the synthesis of the most stable carbenium ion to date. This was accomplished by para-functionalization of TATA+ with electron donating groups to decrease the reduction potential.
OriginalsprogEngelsk
ForlagDepartment of Chemistry, Faculty of Science, University of Copenhagen
Antal sider379
StatusUdgivet - 2024

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