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Author Goll, J. G. ♦ Moore, K. T. ♦ Therien, M. J. ♦ Ghosh, A.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword CHEMISTRY ♦ ZINC COMPLEXES ♦ SYNTHESIS ♦ X-RAY SPECTRA ♦ ELECTROCHEMISTRY ♦ PHOTOCHEMICAL REACTIONS ♦ ORGANOMETALLIC COMPOUNDS ♦ ELECTRONIC STRUCTURE ♦ PHYSICAL CHEMISTRY ♦ BOND ANGLE ♦ BOND LENGTHS ♦ PORPHYRINS ♦ IONIZATION POTENTIAL
Abstract The synthesis, optical spectroscopy, photophysical properties, electrochemistry, and X-ray photoelectron spectroscopy of a series of [5,10,15,20-tetrakis(perfluoroalkyl)porphinato]zinc(II ) complexes and their free base analogs are reported. The title compounds were prepared by a condensation methodology that utilizes perfluoro-1-(2`-pyrrolyl)-1-alkanol precursors and employs continuous water removal throughout the course of the reaction to yield the meso perfluorocarbon-substituted porphyrins. The nature of the porphyrin-pendant meso-perfluoroalkyl group exerts considerable influence over the macrocycle`s solubility properties. The structure of the monopyridyl adduct of [5,10,15,20-tetrakis(heptafluoropropyl)porphinato] zinc(II) features an S{sub 4}-distorted porphyrin core; X-ray data are given. Electrochemical studies carried out on these porphyrin and (porphinato)zinc(II) complexes indicate that meso-perfluoroalkylporphyrins are among the most electron-deficient porphyrinic species known. X-ray photoelectron spectroscopy experiments corroborate the electron poor nature of these systems and evince extreme stabilization of the nitrogen ls orbitals, consonant with particularly effective removal of electron density from the macrocycle by the meso-perfluoroalkyl moieties that is modulated by {sigma}-symmetry orbitals. 27 refs., 8 figs., 6 tabs.
ISSN 00027863
Educational Use Research
Learning Resource Type Article
Publisher Date 1996-09-04
Publisher Place United States
Journal Journal of the American Chemical Society
Volume Number 118
Issue Number 35


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