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
- Univ. of Pennsylvania, Philadelphia, PA (United States)
- Univ., of Tromso (Norway)
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.
- DOE Contract Number:
- FG02-94ER14494
- OSTI ID:
- 380902
- Journal Information:
- Journal of the American Chemical Society, Vol. 118, Issue 35; Other Information: PBD: 4 Sep 1996
- Country of Publication:
- United States
- Language:
- English
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