title: Influence of Meso Substituents on Electronic States of (Oxoferryl)porphyrin pi-Cation Radicals.
abstract: A series of (oxoferryl)porphyrin pi-cation radicals generated from porphyrins substituted at the meso positions with highly electron-withdrawing aryl groups has been characterized: tetrakis-5,10,15,20-(2,6-dichlorophenyl)-, 5-(2-chloro-6-nitrophenyl)-10,15,20-tris(2,6-dichlorophenyl)-, and 5-(2,6-dinitrophenyl)-10,15,20-tris(2,6-dichlorophenyl)porphyrins (porphyrins 1-3, respectively). The physical-chemical properties of the oxidized complexes of 1-3 are compared to those of two (oxoferryl)porphyrin pi-cation radical complexes substituted with electron-releasing aryl groups: tetramesitylporphyrin (TMP) and 2-iodotetramesitylporphyrin (2-iodoTMP). While all of the complexes examined show close correspondance in a number of spectroscopic parameters, some significant differences were observed. In contrast to observations for the oxidized complexes of TMP and 2-iodoTMP, the resonance Raman marker bands nu(2) and nu(11), which are indicators of symmetry state of porphyrin pi-cation radicals of 1-3, do not show the expected downfrequency shifts for oxidation to compound I analogs in a(2u) symmetry states. The upfield hyperfine NMR shifts of the pyrrole beta-proton signals of the compound I analogs of 1-3 are much larger than those for TMP and 2-iodoTMP. These data may be explained by admixture of some a(1u) character into the ground state of radical cations of 1-3, consistent with the hypothesis that electron-withdrawing meso substituents lower the energy of the a(2u) molecular orbital, favoring an a(1u) admixture.
authors.affiliation: Department of Environmental Sciences and Engineering, The University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284, Institut LeBel, Université Louis Pasteur, 67070 Strasbourg, France, and Institut für Physik, Medizinische Universität zu Lübeck, Lübeck, Germany.
authors.forename: K.
authors.initials: K
authors.lastname: Jayaraj
authors.forename: J.
authors.initials: J
authors.lastname: Terner
authors.forename: A.
authors.initials: A
authors.lastname: Gold
authors.forename: D. A.
authors.initials: DA
authors.lastname: Roberts
authors.forename: R. N.
authors.initials: RN
authors.lastname: Austin
authors.forename: D.
authors.initials: D
authors.lastname: Mandon
authors.forename: R.
authors.initials: R
authors.lastname: Weiss
authors.forename: E.
authors.initials: E
authors.lastname: Bill
authors.forename: M.
authors.initials: M
authors.lastname: Müther
authors.forename: A. X.
authors.initials: AX
authors.lastname: Trautwein