Author ORCID Identifier
Document Type
Thesis
Date of Award
4-29-2026
Keywords
photocatalysis, uranyl, direct hydrogen atom transfer, ligand exchange
Degree Name
Chemistry (BA, BS)
Department
CHEMISTRY
First Advisor
Dr. John R. Swierk
Second Advisor
Dr. Claire Besson
Series
Science and Mathematics
Subject Heading(s)
photocatalysis, uranyl, direct hydrogen atom transfer, ligand exchange
Abstract
Uranyl photocatalysts have shown promise in their ability to effect a wide variety of chemical transformations through direct hydrogen atom transfer (d-HAT). They also offer a cheaper and environmentally friendlier alternative to existing ruthenium or iridium photocatalyst designs. These catalysts are defined by inert axial oxo groups and a variable equatorial ligand environment which can modulate key photocatalyst properties such as light absorption and reduction potential. Here we report the synthesis of a novel photocatalyst candidate, UO2(acac)2(4MeNHpy), whose equatorial pyridine ligand is displaced by solvent molecules in acetonitrile through an associative mechanism (ΔGr = 18 kJ/mol ). We show that pyridine lability is common to previously studied catalysts of the type UO2(acac)2(R-pyridine), and that pyridine pKa is a parameter which can predict lability, with more acidic pyridines possessing longer U-N bond lengths. The dehydrogenation of 1-phenylethanol is used as a model reaction to probe the performance of UO2(acac)2(4MeNHpy) in acetonitrile, whose 24 hour yield is within error of that of uranyl nitrate hexahydrate (UNH), the standard uranyl photocatalyst. Compared to UNH, this novel catalyst appears to operate through a distinct mechanism, in which it acts as a precatalyst and decomposes with time.
Recommended Citation
Eaton, Henry, "Properties of and Ligand Dynamics in a Novel Uranyl Photocatalyst" (2026). Undergraduate Honors Theses. 60.
https://orb.binghamton.edu/undergrad_honors_theses/60
