Date of Award


Degree Name

Doctor of Philosophy




Dino Villagrán


In the last decade, photoredox catalysis has become a powerful tool in synthetic chemistry. It relies on the ability of catalytic systems that facilitate energy-demanding redox reactions thanks to photoinduced electron transfer processes. This dissertation focuses on the computational investigation of the redox properties of transition metal photoredox catalysts using density functional theory (DFT) calculations. The research systematically explores the effects of altering redox-active ligands on the thermodynamics of electron transfer events in the photoredox cycle. The electronic structure changes throughout oxidative and reductive quenching cycles are analyzed, with a particular focus on Cu(I) complexes. Through computational techniques, insights into ligand- and metal-centered redox events are obtained, including the impact of flattening distortion on the kinetics and thermodynamics of metal-centered electron transfers of Cu(I) photosensitizers. The influence of ligand modification on the redox properties of photoredox catalysts is also investigated with the aim of establishing structure-activity relationships to guide the discovery and optimization of new photosensitizers. Relationships between the inherent properties of the redox-active ligands and the thermodynamics of the photosensitizers were obtained, opening the door for faster screening techniques to accelerate the discovery of new photosensitizers and optimize their redox properties. The computational protocol for the calculation of reduction potentials was extended to investigate the electrochemical reduction and oxidation of perfluorooctanoic acid (PFOA), addressing environmental concerns surrounding poly and perfluoroalkyl substances (PFAS). This research highlights the potential of the computational method employed herein for the rational design of molecular platforms for catalytic and environmental applications.




Received from ProQuest

File Size

223 p.

File Format


Rights Holder

Christian Fernando Sandoval Pauker

Available for download on Friday, May 23, 2025