Development of iron (III) tetra(meso-aryl)porphyrins and N-annulated perylene diimide tethered rhenium (I) bipyridine supramolecular dyads for carbon dioxide conversion catalysis

Koenig, Joshua David Brock

Development of iron (III) tetra(meso-aryl)porphyrins and N-annulated perylene diimide tethered rhenium (I) bipyridine supramolecular dyads for carbon dioxide conversion catalysis

dc.contributor.advisor	Welch, Gregory
dc.contributor.author	Koenig, Joshua David Brock
dc.contributor.committeemember	Sutherland, Todd
dc.contributor.committeemember	Van Humbeck, Jeffrey
dc.contributor.committeemember	Piers, Warren
dc.contributor.committeemember	Warren, Jeffrey
dc.date	2022-11
dc.date.accessioned	2022-09-09T14:38:08Z
dc.date.available	2022-09-09T14:38:08Z
dc.date.issued	2022-08
dc.description.abstract	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.	en_US
dc.identifier.citation	Koenig, J. D. B. (2022). Development of iron (III) tetra(meso-aryl)porphyrins and N-annulated perylene diimide tethered rhenium (I) bipyridine supramolecular dyads for carbon dioxide conversion catalysis (Doctoral thesis, University of Calgary, Calgary, Canada). Retrieved from https://prism.ucalgary.ca.	en_US
dc.identifier.uri	http://hdl.handle.net/1880/115170
dc.identifier.uri	https://dx.doi.org/10.11575/PRISM/40192
dc.language.iso	eng	en_US
dc.publisher.faculty	Science	en_US
dc.publisher.institution	University of Calgary	en
dc.rights	University of Calgary graduate students retain copyright ownership and moral rights for their thesis. You may use this material in any way that is permitted by the Copyright Act or through licensing that has been assigned to the document. For uses that are not allowable under copyright legislation or licensing, you are required to seek permission.	en_US
dc.subject.classification	Chemistry--Inorganic	en_US
dc.subject.classification	Chemistry--Organic	en_US
dc.subject.classification	Energy	en_US
dc.title	Development of iron (III) tetra(meso-aryl)porphyrins and N-annulated perylene diimide tethered rhenium (I) bipyridine supramolecular dyads for carbon dioxide conversion catalysis	en_US
dc.type	doctoral thesis	en_US
thesis.degree.discipline	Chemistry	en_US
thesis.degree.grantor	University of Calgary	en_US
thesis.degree.name	Doctor of Philosophy (PhD)	en_US
ucalgary.item.requestcopy	true	en_US