Semester

Summer

Date of Graduation

2019

Document Type

Dissertation

Degree Type

PhD

College

Eberly College of Arts and Sciences

Department

Chemistry

Committee Chair

Carsten Milsmann

Committee Co-Chair

Jeffrey L. Petersen

Committee Member

Jeffrey L. Petersen

Committee Member

Jessica M. Hoover

Committee Member

Brian V. Popp

Committee Member

James P. Lewis

Abstract

Early transition metals like zirconium are attractive candidates for the design of luminescent molecules based on earth-abundant elements. Here, a series of zirconium complexes carrying two pyrrolyl-based ligands have been synthesized and characterized. These complexes are photoluminescent upon excitation with visible light and exhibit remarkably long emission lifetimes of hundreds of μs in solution at room temperature. Computational studies using time-dependent density functional theory (TD-DFT) were conducted to identify the nature of the luminescent excited states as mixed intra-ligand/ligand-to-metal charge-transfer (ILCT/LMCT) states. The electrochemistry studies revealed multiple reversible redox events for each zirconium complex. Furthermore, the excited state of the zirconium compounds can serve as strong electron/energy transfer reagents and were utilized to facilitate photoredox catalysis.

Embargo Reason

Publication Pending

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