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dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorD'Souza, Francisen_US
dc.contributor.authorZandler, Melvin E.en_US
dc.contributor.authorTagliatesta, Pietroen_US
dc.contributor.authorOu, Zhongpingen_US
dc.contributor.authorShao, Jianguoen_US
dc.contributor.authorVan Caemelbecke, Ericen_US
dc.contributor.authorKadish, Karl M.en_US
dc.identifier.citationInorganic chemistry. 1998 Sep 7; 37(18): 4567-4572.en_US
dc.descriptionFull text of this article is not available in SOAR.en_US
dc.description.abstractThe electronic, spectral, and electrochemical characterization of (meso-tetraphenylporphyrinato)zinc(II) complexes bearing between 0 and 8 bromo substituents at the beta-pyrrole positions is reported. The investigated compounds are represented as (TPPBr(x)())Zn where TPPBr(x)() is the dianion of brominated 5,10,15,20-tetraphenylporphyrin and x varies between 0 and 8. Each porphyrin undergoes four well-defined one-electron transfer reactions to yield porphyrin pi-cation radicals and dications upon oxidation and porphyrin pi-anion radicals and dianions upon reduction. Half-wave potentials for the first reduction of (TPPBr(x)())Zn can be described by a single linear free energy relationship, and plots of E(1/2) versus the number of Br groups on the complex show a linear correlation with a positive slope of 63 mV per Br group. This is not the case for the other three electron transfer processes of the compounds where plots of E(1/2) versus the number of Br groups show distinctly different linear correlations for derivatives with 0-4 Br groups and those with 4-8 Br groups. The effect of increasing number of Br groups on the spectral and electrochemical properties of the neutral complexes was examined over the whole series of compounds, and these experimental results are compared to results of theoretical calculations by semiempirical molecular orbital AM1 methods using configurational interactions (CI) over the four Gouterman frontier pi-orbitals. The dihedral angle containing the four porphyrin macrocycle ring nitrogens is proposed as a measure of porphyrin ring nonplanarity, and this value increases with increasing number of Br substituents on (TPPBr(x)())Zn. Results of the AM1-CI = 4 calculations indicate that the spectrally determined HOMO-LUMO gap, i.e., the energy corresponding to the low-energy absorption band, varies in a nonlinear fashion with increasing number of Br substituents on the macrocycle and this is due to both the electronic effect of the substituents and the macrocycle nonplanarity. The HOMO-LUMO gaps theoretically calculated by AM1-CI = 4 methods thus parallel values which are experimentally obtained by electrochemistry or spectroscopy. The lack of well-defined linear free energy relationships for all processes except for the first reduction can be explained on the basis of electronic effects caused by the halogen substituents and nonplanar macrocyclic distortions induced by steric interactions among the peripheral substituents. In the case of porphyrin dication formation, the redox potentials are virtually independent of the bromo substituents.en_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesInorganic chemistryen_US
dc.relation.ispartofseriesInorg Chemen_US
dc.titleElectronic, Spectral, and Electrochemical Properties of (TPPBr(x)())Zn Where TPPBr(x)() Is the Dianion of beta-Brominated-Pyrrole Tetraphenylporphyrin and x Varies from 0 to 8en_US
dc.description.versionpeer revieweden_US
dc.rights.holderCopyright © 1998 American Chemical Societyen_US

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