Browsing by Author "Koenig, Joshua David Brock"

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    Development of iron (III) tetra(meso-aryl)porphyrins and N-annulated perylene diimide tethered rhenium (I) bipyridine supramolecular dyads for carbon dioxide conversion catalysis
    (2022-08) Koenig, Joshua David Brock; Welch, Gregory; Sutherland, Todd; Van Humbeck, Jeffrey; Piers, Warren; Warren, Jeffrey
    This dissertation details the development of novel molecular organometallic complexes for applications in carbon dioxide (CO2) conversion catalysis. Chapter One introduces the notion of closing the carbon loop, as well as explores state-of-the-art molecular organometallic complexes based upon the iron (III) tetra(meso-aryl)porphyrin and rhenium (I) (2,2’-bipyridine) tricarbonyl chloride motifs, which are capable of highly selective and highly efficient CO2 conversion catalysis. Structure-property relationships described in this section helped guide the design of next generation organometallic catalysts that will make use of mesomeric effects and second-sphere electronic modifications to achieve improved performance with lower energy unput. Chapter Two explores the influence of mesomeric effects on the iron (III) tetra(meso-aryl)porphyrin platform by switching conventional phenyl-groups with smaller thiophene-based substituents. Although lower electrocatalytic CO2 conversion overpotentials were realized, these iron (III) tetra(meso-thienyl) porphyrins were subject to lower performance. Chapter Three investigates a series of N-annulated perylene diimide tethered rhenium bipyridine dyads. The N-annulated perylene diimide groups were elucidated to act as a second-sphere electron-reservoir for rhenium bipyridine catalyst, where the preferred electrocatalytic pathway was governed by the applied overpotential and the tether length between the two moieties. Chapter Four explores the photocatalytic CO2 conversion abilities of various electronically modified N-annulated perylene diimide tethered rhenium bipyridine dyads. The nature of the electronic substituent changed the preferred photoexcitation pathway, as well as the overall electronic driving-force for electron-transfer in the dyads. Chapter Five examines possible future research directions for these iron (III) tetra(meso-thienyl)porphyrin and N-annulated perylene diimide tethered rhenium (I) tricarbonyl bipyridine supramolecular dyad platforms, and then concludes by discussing the obstacles of closing the carbon loop using catalytic CO2 conversion.