Date of Award

Spring 2020

Document Type

Open Access Dissertation

First Advisor

Aaron K. Vannucci

Abstract

Photocatalysis is a rapidly growing field and a powerful synthetic tool that has recently seen many advancements, showing immense promise to replace classic catalysis with a mild and elegant alternative methodology. Visible light driven catalysis relies on redox stable transition metal and organic based photoactive catalysts (photocatalysts) that absorb visible light efficiently and facilitate electron/energy transfer. The desire for greener and more renewable catalytic methods has caused research to shifted away from traditional transition metals (due to scarcity and environmental toxicity) and toward organic based photocatalysts. Due to similar photophysical and electrochemical characteristics of each of these classes of photocatalysts the organic based photocatalysts have not only shown the capability to replace transition metal catalysts but have been shown to outperform them. To accommodate the diverse demand of photocatalytic systems the systematic tailoring of photocatalyst structure is essential and has allowed the expanding scope of photocatalysis.

In order to meet the growing need for diverse and powerful photocatalysts, the systematic alteration of these compounds has been rapidly growing in literature. The ability to tailor a photocatalyst, organic or transition metal based, to desired electrochemical and photophysical properties by introduction of key functional groups to an established aromatic photocatalysts is key to meeting this demand. Synthesis based on structure and property relationships allows for the systematic tailoring of established photocatalysts. To accomplish this tailoring, functional groups are chosen based on key characteristics such as electron density, halogen groups, and electron donating/withdrawing characteristics, that determine photophysical and electrochemical properties.

In order to effectively replace transition metal photocatalysts, organic photocatalysts need to mirror the photocatalytic capabilities of these complexes. Focusing on photophysical and electrochemical properties of the resulting photocatalysts has allowed the application of organic photocatalysts to a multitude of organic synthesis systems. Furthermore, the instillation of proper functional groups has also facilitated the incorporation of organic photocatalysts into photovoltaic devices and advancing the field of renewable energy.

Included in

Chemistry Commons

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