First Advisor

Buss, Bonnie

First Committee Member

Weinrich, Melissa

Second Committee Member

Watsky, Murielle

Degree Name

Master of Science

Document Type

Thesis

Date Created

12-2025

Department

College of Natural and Health Sciences, Chemistry and Biochemistry, Chemistry and Biochemistry Student Work

Abstract

In photosynthesis, the energy of sunlight is perfectly harnessed to facilitate the production of small molecules that are essential for plant life on earth. Inspired by this model of energy efficiency and simplicity, this work seeks to mimic that ability to use the energy in visible light to perform new and more efficient chemistries. Just like in photosynthesis, photocatalysts can act as chromophores absorbing light to excite electrons opening new pathways for previously untapped reactivity. Recent research has provided a wide range of small molecule reactions that are made possible or easier by the use of a photocatalyst. However, these powerful catalysts can be difficult to recover and recycle. This work outlines the development of two polymer supported photocatalysts (PS-PCs) attached to poly(methyl methacrylate). The purpose of this research is to incorporate an N-aryl phenoxazine photocatalyst motif onto a poly(methyl methacrylate) (PMMA) backbone to increase recoverability.

A synthetic technique was developed to efficiently synthesize these PS-PCs on a small scale. A self-organocatalyzed atom transfer radical polymerization was used to successfully synthesize a range of PS-PCs on a milligram scale. The approach did not necessitate extra catalysts and opened a door to the potential for the development of a self-catalyzed controlled radical polymerization.

The synthesized PS-PCs were then characterized to reveal the potential of structure-property relationships. The photophysical characteristics of the PS-PCs differed based on their connectivity to the polymer support. This indicates that attachment of photocatalysts to a polymer support could not only improve recovery rates but also provide a new handle for structural modification. These structure property relationships could allow for increased rational design of PS-PCs to accomplish desirable small molecule reactions.

The PS-PCs were then tested in model reactions to determine if their unique differences in photophysical properties correlated to new reactivity. These model reactions revealed that the polymer support could in some cases provide a distinct environment for the photocatalyst. This led to differing selectivity in different environments when compared to a molecular photocatalyst. Overall, this work shows a synthesis of PS-PCs with distinct structure-property relationships that yield unique reactivity.

Abstract Format

html

Disciplines

Organic Chemistry | Polymer Chemistry

Keywords

Photocatalysis; polymer; photochemistry; photoredox catalysis; O-ATRP

Language

English

Extent

88 pages

Rights Statement

Copyright is held by the author

Digital Origin

Born digital

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