Structure and redox properties of electropolymerized film obtained from iron meso-tetrakis(3-thienyl)porphyrin

Makoto Yuasa, Kenichi Oyaizu, Aritomo Yamaguchi, Masuhide Ishikawa, Katsuya Eguchi, Tomohiro Kobayashi, Yuujiro Toyoda, Satoshi Tsutsui

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

Oxidative polymerization of bromoiron(III) meso-tetrakis(3-thienyl)porphyrin gave a novel polymeric porphyrin complex randomly crosslinked at the 2,5-positions of the peripheral thienyl groups. The electrical semiconductivity of ca. 10-5 S/cm after I2 doping indicated that the polymer had a π-conjugated structure with a moderate delocalization of π electrons over the thienylporphyrin units. PM3 calculations for free-base models revealed that HOCO (the highest occupied crystal orbital) band width was reduced by introduction of the porphyrin moieties into the thienylene backbone and yet low HOCO-LUCO (the lowest unoccupied crystal orbital) gap was maintained, which accounted for the relatively low electrical conductivity of the porphyrin polymer. The modified electrode prepared by electropolymerization was redox-active due to the presence of iron(II/III) couple and the semiconductivity of the film, which served as a novel non-enzymatic electrochemical sensor for superoxide anion radical based on the facile electrocatalytic oxidation of the superoxide.

Original languageEnglish
Pages (from-to)616-621
Number of pages6
JournalPolymers for Advanced Technologies
Volume16
Issue number8
DOIs
Publication statusPublished - 2005 Aug
Externally publishedYes

Fingerprint

Porphyrins
Iron
Superoxides
Crystals
Polymers
Electrochemical sensors
Electropolymerization
Negative ions
Polymerization
Doping (additives)
Bandwidth
Oxidation
Electrodes
Oxidation-Reduction
Electrons

Keywords

  • Conjugated polymers
  • Electropolymerization
  • Films
  • Porphyrin
  • Structure

ASJC Scopus subject areas

  • Polymers and Plastics

Cite this

Structure and redox properties of electropolymerized film obtained from iron meso-tetrakis(3-thienyl)porphyrin. / Yuasa, Makoto; Oyaizu, Kenichi; Yamaguchi, Aritomo; Ishikawa, Masuhide; Eguchi, Katsuya; Kobayashi, Tomohiro; Toyoda, Yuujiro; Tsutsui, Satoshi.

In: Polymers for Advanced Technologies, Vol. 16, No. 8, 08.2005, p. 616-621.

Research output: Contribution to journalArticle

Yuasa, M, Oyaizu, K, Yamaguchi, A, Ishikawa, M, Eguchi, K, Kobayashi, T, Toyoda, Y & Tsutsui, S 2005, 'Structure and redox properties of electropolymerized film obtained from iron meso-tetrakis(3-thienyl)porphyrin', Polymers for Advanced Technologies, vol. 16, no. 8, pp. 616-621. https://doi.org/10.1002/pat.633
Yuasa, Makoto ; Oyaizu, Kenichi ; Yamaguchi, Aritomo ; Ishikawa, Masuhide ; Eguchi, Katsuya ; Kobayashi, Tomohiro ; Toyoda, Yuujiro ; Tsutsui, Satoshi. / Structure and redox properties of electropolymerized film obtained from iron meso-tetrakis(3-thienyl)porphyrin. In: Polymers for Advanced Technologies. 2005 ; Vol. 16, No. 8. pp. 616-621.
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