INFLUENCE OF PROTON ACCEPTORS ON THE KINETICS OF PHOTOINITATED PROTON TRANSFER AND PROTON-COUPLED ELECTRON TRANSFER REACTIONS
Public Deposited- Last Modified
- September 23, 2019
- Creator
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Lennox, James Christian
- Affiliation: College of Arts and Sciences, Department of Chemistry
- Abstract
- Growing energy needs and greenhouse gas emissions have motivated increasing efforts in efficient and economical renewable fuel production. One possible answer to this challenge comes in the form of light-driven fuel-forming catalysis, wherein low energy molecules are converted to high energy molecules through multi-proton multi-electron reactions driven by absorption of solar photons. Reactions involving the movement of both protons and electrons are termed proton-coupled electron transfer (PCET) reactions, and are difficult to orchestrate for a single proton and electron, and much more challenging for multiple protons and electrons. To that end, research on light-driven single-proton single-electron PCET is needed to better understand this simpler reaction scheme before the more daunting multi-proton multi-electron reactions can be optimized for efficient fuel generation. Within light-driven PCET, two general schemes exist: flash-quench systems in which powerful thermal reactants are generated following light absorption and subsequently undergo PCET reactions in a charge separated state, and excited-state systems in which the PCET reaction occurs directly with reactants in their electronically excited states. This work contains examples of systems intended for each above scheme. Using a flash-quench scheme, a comprehensive kinetic and thermodynamic investigation was performed on a ruthenium-tyrosine dyad that was found to undergo PCET reactions in the presence of base. A novel photoacid was also developed intended for use in excited-state PCET reactions, and its photophysical and photoacidic properties were thoroughly investigated. These studies work to enhance our knowledge of single-proton single-electron PCET and will ultimately help enable the design of efficient systems for multi-proton multi-electron solar-to-fuel transformations.
- Date of publication
- 2019
- Keyword
- DOI
- Resource type
- Advisor
- Lockett, Matthew R
- Meyer, Gerald J
- Meyer, Thomas J
- Atkin, Joanna M
- Dempsey, Jillian L
- Degree
- Doctor of Philosophy
- Degree granting institution
- University of North Carolina at Chapel Hill Graduate School
- Graduation year
- 2019
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