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dc.contributor.advisorBetley, Theodore A
dc.contributor.authorScharf, Austin Bennett
dc.date.accessioned2013-10-15T13:36:03Z
dc.date.issued2013-10-15
dc.date.submitted2013
dc.identifier.citationScharf, Austin Bennett. 2013. First-Row Transition Metal Complexes of Dipyrrinato Ligands: Synthesis and Characterization. Doctoral dissertation, Harvard University.en_US
dc.identifier.otherhttp://dissertations.umi.com/gsas.harvard:11090en
dc.identifier.urihttp://nrs.harvard.edu/urn-3:HUL.InstRepos:11169796
dc.description.abstractA library of variously-substituted dipyrrins and their first-row transition metal (Mn, Fe, Cu, Zn) complexes have been synthesized, and the effects of peripheral substituents on the spectroscopic, electrochemical, and structural properties of both the free-base dipyrrins and their metal complexes has been explored. The optical and electrochemical properties of the free dipyrrins follow systematic trends; with the introduction of electron-withdrawing substituents in the 2-, 3-, 5-, 7-, and 8-positions of the dipyrrin, bathochromic shifts in the absorption spectra are observed, oxidation becomes more difficult, and reduction becomes more facile. Similar effects are seen for iron(II) dipyrrinato complexes, where peripheral substitution of the dipyrrinato ligand induces red-shifts in the absorption spectra and increases the oxidation potential of the bound iron. Steric interactions between the peripheral halogens and the 5-substituent of the dipyrrinato ligand can induce distortion of the ligand from planarity, resulting in widely varying 57Fe Mössbauer quadrupole splitting (|ΔEQ|) parameters.en_US
dc.description.sponsorshipChemistry and Chemical Biologyen_US
dc.language.isoen_USen_US
dash.licenseLAA
dc.subjectChemistryen_US
dc.subjectInorganic chemistryen_US
dc.subjectDipyrrinen_US
dc.subjectLuminescenceen_US
dc.subjectSpectroscopyen_US
dc.subjectSynthesisen_US
dc.subjectTransition metalsen_US
dc.titleFirst-Row Transition Metal Complexes of Dipyrrinato Ligands: Synthesis and Characterizationen_US
dc.typeThesis or Dissertationen_US
dash.depositing.authorScharf, Austin Bennett
dc.date.available2013-10-15T13:36:03Z
thesis.degree.date2013en_US
thesis.degree.disciplineChemistry and Chemical Biologyen_US
thesis.degree.grantorHarvard Universityen_US
thesis.degree.leveldoctoralen_US
thesis.degree.namePh.D.en_US
dc.contributor.committeeMemberJacobsen, Ericen_US
dc.contributor.committeeMemberFriend, Cynthiaen_US
dash.contributor.affiliatedScharf, Austin


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