Electrochemical, Spectroscopic and Acid-base Properties of Pyridylporphyrins in Nonaqueous Media

dc.contributor.advisorKadish, Karl M.
dc.contributor.committeeMemberBear, John L.
dc.contributor.committeeMemberBaldelli, Steven
dc.contributor.committeeMemberTeets, Thomas S.
dc.contributor.committeeMemberVan Caemelbecke, Eric
dc.creatorZhu, Jialiang 1990-
dc.creator.orcid0000-0003-3413-6718
dc.date.accessioned2018-11-30T21:33:11Z
dc.date.available2018-11-30T21:33:11Z
dc.date.createdAugust 2016
dc.date.issued2016-08
dc.date.submittedAugust 2016
dc.date.updated2018-11-30T21:33:12Z
dc.description.abstractThis thesis describes the electrochemical, spectroscopic and acid-base properties of pyridylporphyrins, tetramethylpyridyl porphyrins and corroles in nonaqueous media. Several corroles are also examined. Free-base and metal derivatives (CoII, NiII, CuII and ZnII) of pyridylporphyrins possessing one, two or four pyridyl meso-substituents were examined before, during and after the addition of protons to solution in the form of trifluoroacetic acid (TFA). The free-base (metal-free) pyridylporphyrins undergo an initial protonation on the pyridyl substituents and this is followed by protonation of the central nitrogen atoms in a second step. The pyridylporphyrins with metal centers are only protonated at the meso-pyridyl groups. Both sites of protonation are associated with specific changes in the electrochemical and spectroscopic properties of the compounds. The utilized solvent was shown to have an effect on the protonation constants, which varied from 102 to 104, depending upon the specific compound. The tetrapositively-charged free-base tetra-N-methylpyridylporphyrins possess four Cl-, Br-, I- or PhSO3- counteranions and the electrochemistry of these compounds was examined in DMF or DMSO, containing 0.1 M tetra-n-butylammonium hexafluorophosphate (TBAPF6) or tetra-n-butylammonium iodide (TBAI). These measurements were made in order to study the interaction of the counteranion, the solvent and the supporting electrolyte on the reductions. Finally, the electrochemical properties of iron ferrocenylcorroles with NO, C6H5 or Cl- axial ligands were examined in PhCN containing 0.05 M tetrakis-fluorophenylborate (TFAB).
dc.description.departmentChemistry, Department of
dc.format.digitalOriginborn digital
dc.format.mimetypeapplication/pdf
dc.identifier.urihttp://hdl.handle.net/10657/3570
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.subjectPyridylporphyrin
dc.subjectCorroles
dc.subjectElectrochemistry
dc.subjectAcid-base properties
dc.titleElectrochemical, Spectroscopic and Acid-base Properties of Pyridylporphyrins in Nonaqueous Media
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.levelMasters
thesis.degree.nameMaster of Science

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