Chemistry and Chemical Biology ETDs

Publication Date

Fall 9-23-2021

Abstract

This dissertation reports and examines contributions made in the advancement of inorganic photochemistry. Empirically driven assessments are allotted to the interplay between ligand sets, excited states, and photochemistry observed in metal complexes. A methodical spectroscopic examination is provided for oligothiophene-sensitized lanthanides. Their excited state dynamics were elucidated by femtosecond pump-probe spectroscopy and used to develop a model explaining their wavelength-dependent dual functionality. Iron (II) cyanide and isocyanides are evaluated to identify the efficacy of strong-field ligands in promoting charge-transfer excited states. Fundamentals of ligand field theory helped conceptualize the synthetically tunable parameters and effects transposed to their absorption dynamics. Transition metal sulfimides were developed to address inherent issues with ruthenium sulfoxides and to better understand sulfimide coordination chemistry. Evidence for redox-stimulated linkage-isomerization in ruthenium-sulfimides was corroborated by absorption and electrochemical data. Herein, the developmental strategies, spectroscopic investigations, and analysis of various chromophores are examined to delineate the intricacies involved in inorganic photochemistry.

Keywords

Photochromic, Ruthenium, Iron, Isomerization, Charge Transfer, Polypyridyl

Document Type

Dissertation

Degree Name

Chemistry

Level of Degree

Doctoral

Department Name

Department of Chemistry and Chemical Biology

First Committee Member (Chair)

Jeffrey J. Rack

Second Committee Member

Martin L. Kirk

Third Committee Member

David G. Whitten

Fourth Committee Member

Dongchang Chen

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