Electrochemical and Spectroelectrochemical Studies of Dipyrrolylquinoxaline, Porphyrins and Pyrazinoporphyrazines

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dc.contributor.advisorKadish, Karl M.
dc.contributor.committeeMemberBaldelli, Steven
dc.contributor.committeeMemberBear, John L.
dc.contributor.committeeMemberBriggs, James M.
dc.contributor.committeeMemberCarrasquillo M., Edwin
dc.creatorFu, Zhen 1981-
dc.date.accessioned2014-07-09T15:40:52Z
dc.date.available2014-07-09T15:40:52Z
dc.date.createdMay 2012
dc.date.issued2012-05
dc.date.updated2014-07-09T15:40:52Z
dc.description.abstractIn this Dissertation, the redox and UV-visible spectroscopic properties of a series of dipyrrolylquinoxalines, porphyrins and pyrazinoporphyraines are characterized in nonaqueous solvents. Electron-transfer reduction mechanisms and acid-base properties of dipyrrolylquinoxaline and its nitro-substituted derivatives are studied in PhCN and MeCN have been examined by means of cyclic voltammetry, UV-visible, NMR and ESR spectroscopy. Disproportionation reactions are coupled with the electron transfer reduction processes of the dipyrrolylquinoxalines to give the pi-anion radical. Tris- and tetrakis-quinoxalinoporphyrins and metal complexes, i.e. (PQ3)M and (PQ4)M, where M = H2II, CuII, PdII, NiII, ZnII, or AuIIIPF6 were also investigated by cyclic voltammetry and thin-layer spectroelectrochemistry in CH2Cl2, PhCN and pyridine. Stable antiaromatic 16 pi,17 pi-electron porphyrinoid CuII and ZnII complexes of tetraphenyltetrabenzoporphyrin (TPTBP) were also characterized in CH2Cl2 or PhCN. Finally, the electrochemical and spectroelectrochemical behavior of a new series of tetra-2,3-pyrazinoporphyrazines were investigated in DMSO, DMF and pyridine. These compounds are represented as [Th8TPyzPzM] where Th8TPyzPz = the tetrakis-2,3-[5,6-di-(2-thienyl)-pyrazino]porphyrazino anion and M = MgII(H2O), CoII, CuII, ZnII or H2I. The related pentametallic species having the formula [(PtCl2)4Py8TPyzPzM], M = PdII, PtII, CdII, CuII, ZnII, MgII, were also investigated in DMSO, DMF and pyridine and described in this Dissertation.
dc.description.departmentChemistry, Department of
dc.format.digitalOriginborn digital
dc.format.mimetypeapplication/pdf
dc.identifier.urihttp://hdl.handle.net/10657/601
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.subjectDipyrrolylquinoxaline
dc.subjectPorphyrins
dc.subjectPorphyrazines
dc.subject.lcshChemistry, Physical and theoretical
dc.titleElectrochemical and Spectroelectrochemical Studies of Dipyrrolylquinoxaline, Porphyrins and Pyrazinoporphyrazines
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.majorPhysical Chemistry
thesis.degree.nameDoctor of Philosophy

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