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Title: Synthesis, structure, electronic spectroscopy, photophysics, electrochemistry, and X-ray photoelectron spectroscopy of highly-electron-deficient [5,10,15,20-tetrakis(perfluoroalkyl)porphinato]zinc(II ) complexes and their free base derivatives

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.

Authors:
; ;  [1];  [2]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Univ., of Tromso (Norway)
Publication Date:
OSTI Identifier:
380902
DOE Contract Number:  
FG02-94ER14494
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 118; Journal Issue: 35; Other Information: PBD: 4 Sep 1996
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; ZINC COMPLEXES; SYNTHESIS; X-RAY SPECTRA; ELECTROCHEMISTRY; PHOTOCHEMICAL REACTIONS; ORGANOMETALLIC COMPOUNDS; ELECTRONIC STRUCTURE; PHYSICAL CHEMISTRY; BOND ANGLE; BOND LENGTHS; PORPHYRINS; IONIZATION POTENTIAL

Citation Formats

Goll, J G, Moore, K T, Therien, M J, and Ghosh, A. Synthesis, structure, electronic spectroscopy, photophysics, electrochemistry, and X-ray photoelectron spectroscopy of highly-electron-deficient [5,10,15,20-tetrakis(perfluoroalkyl)porphinato]zinc(II ) complexes and their free base derivatives. United States: N. p., 1996. Web. doi:10.1021/ja9610904.
Goll, J G, Moore, K T, Therien, M J, & Ghosh, A. Synthesis, structure, electronic spectroscopy, photophysics, electrochemistry, and X-ray photoelectron spectroscopy of highly-electron-deficient [5,10,15,20-tetrakis(perfluoroalkyl)porphinato]zinc(II ) complexes and their free base derivatives. United States. doi:10.1021/ja9610904.
Goll, J G, Moore, K T, Therien, M J, and Ghosh, A. Wed . "Synthesis, structure, electronic spectroscopy, photophysics, electrochemistry, and X-ray photoelectron spectroscopy of highly-electron-deficient [5,10,15,20-tetrakis(perfluoroalkyl)porphinato]zinc(II ) complexes and their free base derivatives". United States. doi:10.1021/ja9610904.
@article{osti_380902,
title = {Synthesis, structure, electronic spectroscopy, photophysics, electrochemistry, and X-ray photoelectron spectroscopy of highly-electron-deficient [5,10,15,20-tetrakis(perfluoroalkyl)porphinato]zinc(II ) complexes and their free base derivatives},
author = {Goll, J G and Moore, K T and Therien, M J and Ghosh, A},
abstractNote = {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.},
doi = {10.1021/ja9610904},
journal = {Journal of the American Chemical Society},
number = 35,
volume = 118,
place = {United States},
year = {1996},
month = {9}
}