Boron-Nitrogen Analogues of Indene Containing Hydrocarbons

Morgan, Matthew Michael

Boron-Nitrogen Analogues of Indene Containing Hydrocarbons

dc.contributor.advisor	Piers, Warren E.
dc.contributor.author	Morgan, Matthew Michael
dc.contributor.committeemember	Roesler, Roland
dc.contributor.committeemember	Sutherland, Todd C.
dc.contributor.committeemember	Hubert, Casey R. J.
dc.contributor.committeemember	Gilroy, Joe B.
dc.date	2019-11
dc.date.accessioned	2019-07-10T18:23:51Z
dc.date.available	2019-07-10T18:23:51Z
dc.date.issued	2019-07-09
dc.description.abstract	Boron-nitrogen (BN) containing polycyclic aromatic hydrocarbons represent an important class of compounds of fundamental and applied interest. Despite their prevalence in main group chemistry, there remain few ways to efficiently synthesize large quantities of BN containing aromatic species. We developed a method for the preparation of 3-bora-9aza-indene heterocycles based on zirconocene mediated functionalization of the ortho-CH bonds of pyridines. Unlike other methods, the boron center in these heterocycles remains functionalized with a chloride ligand allowing the compounds to be further elaborated through halide abstraction or reduction. The utility of the method was demonstrated by applying it towards the preparation of 1,5-dibora-4a,8a-diaza BN analogs of the intriguing hydrocarbon s-indacene starting from 2,5-dimethylpyrazine. This allowed us to experimentally and computationally compare the BN doped derivative to the all-carbon analogue, providing new knowledge on the effect of main group substitutions on bonding in aromatic compounds. The developed synthetic method also provided us access to a new BN doped indenide species in large scale that allowed for its reactivity to be examined in depth. It was found that the reactivity of the nucleophilic indenide depended on which electrophile it was treated with. This divergent reactivity was investigated through reactions with alkyl halides and carbon dioxide and the mechanisms determined were supported through computational methods. Inspired by the properties of the indacene species, we targeted derivatives of BN doped dihydroindeno[1,2-b]fluorene. They were synthesized via electrophilic borylation, a mildly air-sensitive technique, and the end products were handled readily under atmospheric conditions. Through transmetallation via diarylzinc reagents a series of derivatives were synthesized which show broad absorption profiles and frontier energy levels amenable to their use in organic solar cell devices. Exploratory device parameters were studied and show moderate results with PCEs reaching 2% showing the possibility of molecules containing this framework in organic electronic devices.	en_US
dc.identifier.citation	Morgan, M. M. (2019). Boron-Nitrogen Analogues of Indene Containing Hydrocarbons (Doctoral thesis, University of Calgary, Calgary, Canada). Retrieved from https://prism.ucalgary.ca.	en_US
dc.identifier.doi	http://dx.doi.org/10.11575/PRISM/36723
dc.identifier.uri	http://hdl.handle.net/1880/110608
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	Boron	en_US
dc.subject	Main-group	en_US
dc.subject.classification	Education--Sciences	en_US
dc.subject.classification	Engineering--Chemical	en_US
dc.title	Boron-Nitrogen Analogues of Indene Containing Hydrocarbons	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