π-complex formation in electron-transfer reactions of porphyrins

Shunichi Fukuzumi, Taku Hasobe, Kei Ohkubo, Maxwell J. Crossley, Prashant V. Kamat, Hiroshi Imahori

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

π-Complex formation between porphyrins and their radical cations plays an important role in self-exchange electron transfer between neutral porphyrins and the radical cations, leading to negative activation enthalpies when the stabilization energy of the π-complex is larger than the activation energy for the intracomplex electron transfer in the π-complex. A number of porphyrin molecules are self-organized on three-dimensional gold nanoclusters to form monolayer-protected gold nanoclusters (MPCs) that act as an efficient photocatalyst for the uphill reduction of HV2+ by BNAH to produce l-benzylnicotinamidinium ion (BNA+) and hexyl viologen radical cation (HV.+). Such three-dimensional architectures of porphyrin MPCs with large surface area allow supramolecular π-complexation between MPCs and HV+2, resulting in fast electron transfer from the singlet excited state of porphyrin to HV2+ on MPCs. The π-π interaction is exploited to develop efficient photovoltaic devices consisting of porphyrin and fullerene assemblies which have an enhanced light-harvesting efficiency throughout the solar spectrum together with a highly efficient conversion of the harvested light into electrical energy.

Original languageEnglish
Pages (from-to)191-200
Number of pages10
JournalJournal of Porphyrins and Phthalocyanines
Volume8
Issue number1-3
Publication statusPublished - 2004
Externally publishedYes

Fingerprint

Porphyrins
Nanoclusters
Gold
Electrons
Monolayers
Cations
Viologens
Fullerenes
Photocatalysts
Complexation
Excited states
Enthalpy
Stabilization
Activation energy
Chemical activation
Ions
Molecules

Keywords

  • π-complex
  • Electron transfer
  • Fullerene
  • Photovoltaic cell
  • Porphyrin dendrimer

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Fukuzumi, S., Hasobe, T., Ohkubo, K., Crossley, M. J., Kamat, P. V., & Imahori, H. (2004). π-complex formation in electron-transfer reactions of porphyrins. Journal of Porphyrins and Phthalocyanines, 8(1-3), 191-200.

π-complex formation in electron-transfer reactions of porphyrins. / Fukuzumi, Shunichi; Hasobe, Taku; Ohkubo, Kei; Crossley, Maxwell J.; Kamat, Prashant V.; Imahori, Hiroshi.

In: Journal of Porphyrins and Phthalocyanines, Vol. 8, No. 1-3, 2004, p. 191-200.

Research output: Contribution to journalArticle

Fukuzumi, S, Hasobe, T, Ohkubo, K, Crossley, MJ, Kamat, PV & Imahori, H 2004, 'π-complex formation in electron-transfer reactions of porphyrins', Journal of Porphyrins and Phthalocyanines, vol. 8, no. 1-3, pp. 191-200.
Fukuzumi S, Hasobe T, Ohkubo K, Crossley MJ, Kamat PV, Imahori H. π-complex formation in electron-transfer reactions of porphyrins. Journal of Porphyrins and Phthalocyanines. 2004;8(1-3):191-200.
Fukuzumi, Shunichi ; Hasobe, Taku ; Ohkubo, Kei ; Crossley, Maxwell J. ; Kamat, Prashant V. ; Imahori, Hiroshi. / π-complex formation in electron-transfer reactions of porphyrins. In: Journal of Porphyrins and Phthalocyanines. 2004 ; Vol. 8, No. 1-3. pp. 191-200.
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