Synthetic, electrochemical, optical, and conductivity studies of coordination polymers of iron, ruthenium, and osmium octaethylporphyrin

James P. Collman, John McDevitt, Charles R. Leidner, Gordon T. Yee, Jerry B. Torrance, William A. Little

Research output: Contribution to journalArticle

Abstract

A series of ligand-bridged metalloporphyrin polymers, [M(OEP)(L-L)]n (M = Fe, Ru, Os; L-L = pyrazine, 4,4′-bipyridine, 1,4-diazabicyclo[2.2.2]octane), have been synthesized and characterized. When partially oxidized, these polymers are highly conductive. The conductivity of these polymers depends on the extent of doping, the nature of the central transition metal, and the bridging ligand. The doped polymers exhibit strong infrared absorptions due to mixed-valence transitions, the features of which correlate with the bulk conductivity. The infrared spectra of the doped [Os(OEP)(pyz)]n samples reveal the presence of a coupling between an IR-silent vibrational mode of the bridging ligand and a mixed-valence transition, which suggests that the bridging ligand participates in the conduction process. Electrochemical studies of the polymers have been carried out with carbon cloth electrodes. These studies demonstrate that the doping reactions are metal-centered and corroborate the assertion that the porphyrin π-electrons are not involved in the conduction pathway. This feature contrasts with most of the previous work with porphyrinic conductors in which the conduction pathway is dominated by the macrocycle.

Original languageEnglish (US)
Pages (from-to)4606-4614
Number of pages9
JournalJournal of the American Chemical Society
Volume109
Issue number15
StatePublished - 1987

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Osmium
Ruthenium
Polymers
Iron
Ligands
Metals
Doping (additives)
Metalloporphyrins
Pyrazines
Porphyrins
Infrared absorption
Transition metals
Electrodes
Carbon
octaethylporphyrin
Electrons
Infrared radiation

ASJC Scopus subject areas

  • Chemistry(all)

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Synthetic, electrochemical, optical, and conductivity studies of coordination polymers of iron, ruthenium, and osmium octaethylporphyrin. / Collman, James P.; McDevitt, John; Leidner, Charles R.; Yee, Gordon T.; Torrance, Jerry B.; Little, William A.

In: Journal of the American Chemical Society, Vol. 109, No. 15, 1987, p. 4606-4614.

Research output: Contribution to journalArticle

Collman, James P. ; McDevitt, John ; Leidner, Charles R. ; Yee, Gordon T. ; Torrance, Jerry B. ; Little, William A. / Synthetic, electrochemical, optical, and conductivity studies of coordination polymers of iron, ruthenium, and osmium octaethylporphyrin. In: Journal of the American Chemical Society. 1987 ; Vol. 109, No. 15. pp. 4606-4614.
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AU - Little, William A.

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