Date of Award

2025

Degree Type

Dissertation

Degree Name

Doctor of Philosophy in Chemistry

Department

Chemistry

First Advisor

Dugan Hayes

Abstract

Anthracenes and acridines are among the simplest visible light absorbing heterocyclic and polycyclic aromatic hydrocarbons and as such are extensively used in a variety of applications including photosensitizers and fluorescent sensors. Although the photophysics of some derivatives have been studied in the past, there is still a lot of unknown fundamental information that is vital in order to optimize these molecules for particular applications. Transient absorption spectroscopy was used to study the photophysics of the 9-substituted methyl, hydroxymethyl and formyl derivatives of acridine and anthracene. The growth and decay of the triplet-triplet absorption peak were quantified for each dye in order to determine the intersystem crossing rate. Results of this study show the effect of heteroatoms on the spin-orbit coupling of the molecules.

Anthraquinones are also robust dyes within the same family as the anthracenes. They have been studied to undergo a variety of photoreactions such as photodealkylation and cyclization depending on the substituents. Transient absorption spectroscopy was used to observe the formation of the potential photoproducts of 1-methoxyanthraquinone, which solely undergoes photodealkylation to 1-hydroxyanthraquinone and 1-allyloxyanthraquinone, which can additionally undergo intramolecular cyclization. These measurements coupled with photoreactor studies showed a unique example of non-Kasha photochemistry, where 1-allyloxyanthraquinone produces different photoproducts depending on the excitation wavelength.

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