Spectroscopic investigations of perfluoroarene: Arene interactions in solution involving hexafluorobenzene

Abstract

This thesis focuses on common spectroscopic techniques to measure the photophysical consequences of perfluoroarene:arene interactions in solution. The perfluoroarene in these studies was hexafluorobenzene (C6F 6) since it structurally and electronically represents the simplest of all perfluorinated aromatic molecules. The goal of this thesis was to create a library of perfluoroarene:arene interactions and use them to influence chemical reactivity in the excited state both efficiently and predictably. The first chapter outlines the spectroscopic techniques employed, and explains the foundation of this project from solid-state applications. The remaining chapters detail perfluoroarene:arene interactions observed, spectroscopically, in solution. Chapter 2 is a thorough study on the pre-association of pyrene:C6F6 and the impact C6F6 had on the photophysics of dilute and concentrated pyrene solutions. The third chapter summarizes the photophysical results from a variety of rigid polyaromatic molecules, and one flexible polyaromatic (biphenyl). A practical application of this work was observed with nanosecond laser flash photolysis studies outlined in Chapter 4, while the search for other practical applications with quantum dots, oxygen- and carbon-centered radicals in the presence of C6F 6 is detailed in Chapter 5.