Boron Subnaphthalocyanines: The First Unsubstituted Examples, New Boron Lewis Acids, Random Bay Position Halogenation, and Computational Material Screening

Boron subnaphthalocyanines (BsubNcs) are a class of materials that our lab has shown to be alloyed mixtures of derivatives that are randomly chlorinated in the bay positions, resulting from their formation from boron trichloride. These alloyed mixtures were shown to have a positive influence on the functionality of organic photovoltaics whereby an increase in the amount of bay position chlorination was found to increase power conversion efficiency. The bay position chlorinated BsubNcs were also found to be stable in the ambient environment within organic solar cells which also justified their further development. The alloying of these materials leads to a potentially unique opportunity to tailor the alloyed mixture for a desired application by blending pure or partially separated samples of BsubNcs. Herein we lay the groundwork for achieving this goal. We explore the separation of bay position halogenated (chlorinated and brominated) BsubNcs enabled by their functionalization with phenolic axial moieties. We develop an understanding of the dependence of their physical properties on the frequency of bay position halogenation and developed improved analytical techniques for this class of materials. We also present a new method for the synthesis of BsubNcs that circumvents the generation of bay position halogenated species, resulting in the first examples of pure unsubstituted BsubNcs. To achieve this, we proposed that a non-halide boron based Lewis acid is required, and that a balance of the Lewis acidity of the boron source and the Lewis basicity of the BsubNc precursor can guide the synthesis of BsubNcs. After achieving this desired outcome, we also explored the application of this method for the synthesis of the related boron subphthalocyanines (BsubPcs) and as the macrocycles were formed, we found potential for the broad application of this methodology. A computationally calibrated model to screen key material properties of BsubPcs for their accelerated development was also developed. We uniquely found a method that can achieve this with a standard laptop and software that is free to academia. We anticipate that incorporation of BsubNcs into the model will be possible as the key material properties have been determined for BsubNcs developed in this thesis.

Department dc:contributor.department

Chemistry

Year dc:date.issued

2021

Author dc:creator

• Holst, Devon Patrick

Advisor dc:contributor.advisor

• Bender, Timothy P

• Borate
• Boron
• Boron Subnaphthalocyanine
• Macrocycle
• Materials Chemistry
• Organic Electronics

Statement dc:rights

• Attribution 4.0 International

Licence dc:rights.uri

• http://creativecommons.org/licenses/by/4.0/

Handle dc:identifier.uri

http://hdl.handle.net/1807/125877

OAI identifier oai:identifier

oai:utoronto.scholaris.ca:1807/125877