Electrochemistry of Porphyrinoids and Tetrapyrrole Triple-Decker Complexes

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dc.contributor.advisorKadish, Karl M.
dc.contributor.committeeMemberCzernuszewicz, Roman S.
dc.contributor.committeeMemberBaldelli, Steven
dc.contributor.committeeMemberGuloy, Arnold M.
dc.contributor.committeeMemberBriggs, James M.
dc.creatorJiang, Xiaoqin 1989-
dc.date.accessioned2019-09-18T19:37:29Z
dc.date.available2019-09-18T19:37:29Z
dc.date.createdDecember 2016
dc.date.issued2016-12
dc.date.submittedDecember 2016
dc.date.updated2019-09-18T19:37:30Z
dc.description.abstractThis dissertation describes the electrochemistry and spectroelectrochemistry of porphyrinoids and tetrapyrrole triple-decker complexes, which were examined in nonaqueous media using electrochemical techniques in combination with spectroelectrochemical analysis as a function of the central metal ions, the axial ligands, the π-conjugated macrocycles, the peripheral substituents as well as solution conditions. Examined macrocyclic compounds in this dissertation are (i) meso-nitrophenyl metalloporphyrins; (ii) meso-diphosphorylated metalloporphyrins; (iii) unsymmetrical mono-benzoporphyrins; (iv) push-pull opp-dibenzoporphyrins; (v) phthalocyanine-corrole and phthalocyanine-porphyrin triple-decker complexes. In addition to two ring-centered reductions and two ring-centered oxidations, the meso-nitrophenyl metalloporphyrins exhibit reductions of the electroactive NO2Ph groups with a first reversible one-electron-addition followed by one or more irreversible reductions at more negative potentials. The meso-diphosphrylated porphyrins exhibit a slow chemical reaction after the second ring-centered reduction, forming a redox-active phlorin anion which can either be re-oxidized back to the initial porphyrin or be further reduced to form the phlorin dianion. The β, β’-fused mono-benzoporphyrin and opp-dibenzoporphyrin possess smaller HOMO-LUMO gaps and red-shifted and broadened absorption bands compared to those of the corresponding non-benzo porphyrin derivatives, due to the extension of the π-system. The Pc-M-Cor-M-Pc triple-decker complexes bearing nitrophenyl groups on the corrole unit exhibit 5 oxidations and 3-5 reductions depending on the number of the redox-active NO2Ph groups. However, the Pc-M-Pc-M-Por triple-deckers exhibit 4 oxidations and 3 reductions with the first oxidation and the first reduction both being assigned as a one-electron-transfer process on the Pc macrocycle.
dc.description.departmentChemistry, Department of
dc.format.digitalOriginborn digital
dc.format.mimetypeapplication/pdf
dc.identifier.urihttps://hdl.handle.net/10657/4861
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. Further transmission, reproduction, or presentation of this work is prohibited except with permission of the author(s).
dc.subjectElectrochemistry
dc.subjectSpectroelectrochemistry
dc.subjectPorphyrinoids
dc.subjectTetrapyrrole triple-decker complexes
dc.subjectNitrophenyl porphyrin
dc.subjectPhosphorylate porphyrin
dc.subjectBenzoporphyrin
dc.subjectPhthalocyanine/porphyrin triple-deckers
dc.subjectPhthalocyanine/corrole triple-deckers
dc.titleElectrochemistry of Porphyrinoids and Tetrapyrrole Triple-Decker Complexes
dc.type.dcmiText
dc.type.genreThesis
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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