Graduation Year

2026

Document Type

Thesis

Degree

M.S.

Degree Name

Master of Science (M.S.)

Degree Granting Department

Chemistry

Major Professor

Randy Larsen, Ph.D.

Committee Member

Kirpal Bisht, Ph.D.

Committee Member

Arjan van der Vaart, Ph.D.

Committee Member

Stanley Stevens, Ph.D.

Keywords

Photophysics, Monodentate, MOF's, Bidentate, Confinement

Abstract

Ruthenium (II) polypyridyl complexes have emerged as a prominent class of compounds in inorganic photochemistry due to their structural robustness, reversible redox chemistry, and tunable excited-state dynamics. Central to the investigation of these systems is the ability to manipulate the triplet metal-to-ligand charge transfer state (3MLCT). In the context of photoactivated chemotherapy (PACT), the strategic deactivation of this MLCT state to populate a dissociative triplet ligand field state (3LF) can enable the controlled, light-triggered release of caged cytotoxic agents. This work focuses on understanding the caging mechanism of various ligands to optimize the eventual delivery of cytotoxic ligands. In this study, a plug-and-play methodology was employed to generate a library of Ru (II) polypyridyl complexes. By modulating the electron-donating and accepting abilities of the ligands, the resulting emission profiles, excited-state lifetimes, and mechanisms for ligand dissociation were characterized. A primary focus was placed on comparing monodentate versus bidentate ligands to determine their specific photorelease mechanisms. To further refine the delivery specificity, these complexes were also encapsulated within porous metal organic frameworks (MOFs), specifically MOFs USF-2, MOF-5, and MOF-177. This research evaluates how the distinct electrostatic environments and pore geometries of these frameworks influence the excited-state behavior and release profile of the guest complexes. The results demonstrate that the tunable coordination chemistry and MOF encapsulation provide a promising strategy for highly localized, light-triggered medicinal treatments.

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