Chemistry and Chemical Biology ETDs

Publication Date

Fall 9-1-2023

Abstract

Within this dissertation, two distinct classes of metal complexes have been discussed that bear significance in the field of solar energy conversion, photo redox catalysis and memory devices. The first class of the metal complexes is a series of photochromic Ruthenium polypyridyl N-heterocyclic carbene tethered sulfoxide complexes that are reported to undergo unusually slow isomerization from S-bonded to O-bonded and unusually fast thermal reversion from O-bonded to S-bonded configuration. The role of NHC in the excited state dynamics of these complexes have been discussed in detail in Chapter 3.

For the first time in two decades, structural information of the O-bonded configuration of the Ruthenium sulfoxide complex, [Ru(bpy)2(DMSO)2][B(Ph)4]2 resulting from the photo triggered isomerization of an S-bonded [Ru(bpy)2(DMSO)2][B(Ph)4]2 in solid state has been revealed using Photo Crystallography and is discussed in detail in Chapter 4.

In chapter 5, a series of homoleptic Iron complexes is reported to exhibit the longest-lived excited states resulting from charge transfer reported in the literature to date. TD-DFT calculations suggest that the long-lived excited state originates from mixing of 3LC/3MLCT or 5/7MLCT excited state formation or both.

Upon replacing one of the polypyridyl ligands with three -CN ligands, the lifetime of the Iron complexes was shortened to a few ps. Chapter 6 discusses these heteroleptic complexes in detail.

Language

English

Keywords

photoactive, ruthenium polypyridyl, iron polypyridyl

Document Type

Dissertation

Degree Name

Chemistry

Level of Degree

Doctoral

Department Name

Department of Chemistry and Chemical Biology

First Committee Member (Chair)

Dr. Jeffrey J. Rack

Second Committee Member

Dr. David Whitten

Third Committee Member

Dr. Matthew Aronoff

Fourth Committee Member

Dr. Dongchang Chen

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