A Renaissance of the (Anti)Aromaticity Concept in Modern Applications of Organic Chemistry

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dc.contributor.advisorWu, Judy I-Chia
dc.contributor.committeeMemberMay, Jeremy A.
dc.contributor.committeeMemberCai, Chengzhi
dc.contributor.committeeMemberTeets, Thomas S.
dc.contributor.committeeMemberGrabow, Lars C.
dc.creatorWen, Zhili
dc.creator.orcid0000-0001-5678-0163
dc.date.accessioned2022-06-18T23:50:08Z
dc.date.createdAugust 2021
dc.date.issued2021-08
dc.date.submittedAugust 2021
dc.date.updated2022-06-18T23:50:09Z
dc.description.abstractThis dissertation focuses on applying computational quantum chemical tools to explore modern applications of aromaticity and antiaromaticity in organic chemistry. Even though all sophomore organic chemistry students learn about the concepts of aromaticity and antiaromaticity, these ideas continue to find exciting applications in active areas of research. The topics covered in this dissertation include understanding the effects of supramolecular self-assembly on the electronic properties of organic pigments and understanding the origin of acidity differences in popular photoacids. We found that organic pigments with bifunctional hydrogen bonding sites, such as indigo, isoindigo, diketopyrrolopyrrole, and naphthodipyrrolidone, can self-assemble through hydrogen bonding interactions, showing increased [4n] π-electron antiaromaticity and lower LUMO energy levels. The reciprocal relationship between hydrogen bonding and antiaromaticity gain makes them good candidates for components of n-type organic field-effect transistor (OFET) materials. We found that π-polarization of acridone compounds can perturb the numbers and positions of Clar sextet rings. Decreasing numbers of Clar sextets are connected to experimental observations of a narrowing HOMO-LUMO gap and increased charge mobility in hydrogen-bonded assemblies of quinacridone and epindolidione. We also found that many organic acids that are Hückel aromatic in the ground state can convert to Baird antiaromatic in the excited state, triggering facile proton transfer. Stronger photoacids show enhanced “antiaromaticity relief” upon releasing a proton. Together this series of works highlight examples of the underlying effects of (anti)aromaticity in organic chemistry and increase chemical understanding.
dc.description.departmentChemistry, Department of
dc.format.digitalOriginborn digital
dc.format.mimetypeapplication/pdf
dc.identifier.citationPortions of this document appear in: Wen, Zhili, I. Judy, and Chia Wu. "Antiaromaticity gain increases the potential for n-type charge transport in hydrogen-bonded π-conjugated cores." Chemical Communications 56, no. 13 (2020): 2008-2011; and in: Wen, Zhili, Lucas José Karas, Chia-Hua Wu, I. Judy, and Chia Wu. "How does excited-state antiaromaticity affect the acidity strengths of photoacids?." Chemical Communications 56, no. 60 (2020): 8380-8383.
dc.identifier.urihttps://hdl.handle.net/10657/9389
dc.language.isoeng
dc.rightsThe author of this work is the copyright owner. UH Libraries and the Texas Digital Library have their permission to store and provide access to this work. UH Libraries has secured permission to reproduce any and all previously published materials contained in the work. Further transmission, reproduction, or presentation of this work is prohibited except with permission of the author(s).
dc.subjectAromaticity
dc.subjectAntiaromaticity
dc.subjectOrganic Chemistry
dc.subjectComputational Chemistry
dc.titleA Renaissance of the (Anti)Aromaticity Concept in Modern Applications of Organic Chemistry
dc.type.dcmiText
dc.type.genreThesis
dcterms.accessRightsThe full text of this item is not available at this time because the student has placed this item under an embargo for a period of time. The Libraries are not authorized to provide a copy of this work during the embargo period.
local.embargo.lift2023-08-01
local.embargo.terms2023-08-01
thesis.degree.collegeCollege of Natural Sciences and Mathematics
thesis.degree.departmentChemistry, Department of
thesis.degree.disciplineChemistry
thesis.degree.grantorUniversity of Houston
thesis.degree.levelDoctoral
thesis.degree.nameDoctor of Philosophy

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