Organometallic uranyl complexes for photocatalytic C-H bond activation and functionalization
- Rutkauskaite, Ryte
- Advisor(s): Arnold, Polly L
Abstract
Chapter one discusses the synthesis and characterization of novel complexes of the uranyl(VI) ion with a substituted phenanthroline ligand ph2phen. The complexes are investigated by electronic and vibrational spectra and their solid-state structures are presented. Luminescence spectra and lifetimes are determined. Density functional theory (DFT) calculations are carried out to investigate the electronic structure of the complexes in the ground and excited states.
Chapter two discusses the photocatalytic reactivity of the new uranyl complexes in alkane fluorination, oxidation and C-C coupling reactions. Visible light mediated functionalization of the C-H bond in the substrate is achieved through hydrogen atom abstraction. The identity of the photocatalyst is investigated for the fluorination reactions. DFT calculations are performed to compare reaction energy barriers for different photocatalysts and gauge the interactions between the substrate and ph2phen ligand. Finally, Stern-Volmer analyses are performed to determine the nature of collisional quenching between the substrate and the photocatalyst.