Multiporphyrin arrays with π-π Interchromophore interactions

Yuichi Terazono, Gerdenis Kodis, Mirianas Chachisvilis, Brian R. Cherry, Maxime Fournier, Ana L Moore, Thomas A Moore, John Devens Gust

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

A recently reported synthetic method has been employed to prepare several arrays of free base and zinc porphyrins. In the arrays, the porphyrins are arranged around a central benzene ring. The lack of aryl rings in the linkages to the central benzene ring, coupled with the presence of only one meso-aryl substituent on each porphyrin, allows strong electronic interactions between the porphyrin macrocycles. In arrays containing two or six porphyrins, a variety of evidence indicates that the porphyrins exist as twist-stacked dimers reminiscent of the special pairs of bacteriochlorophylls found in some photosynthetic bacteria. These dimers feature van der Waals contact between the macrocycles, and demonstrate excitonic splitting due to π-π interactions. The excitonic effects split and blue-shift the Soret absorptions, and slightly broaden the Q-band absorptions and shift them to longer wavelengths. The interactions also lower the first oxidation potentials by ca. 100 mV, and the arrays show evidence for delocalization of the radical cation over both porphyrins in the dimer. The arrays demonstrate singlet-singlet energy transfer among the chromophores. Arrays of this type will be good models for some aspects of the interactions of photosynthetic pigments, including those of reaction center special pairs and possibly quantum coherence effects. They can also be useful in artificial photosynthetic constructs.

Original languageEnglish
Pages (from-to)245-258
Number of pages14
JournalJournal of the American Chemical Society
Volume137
Issue number1
DOIs
Publication statusPublished - Jan 14 2015

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Porphyrins
Dimers
Benzene
Bacteriochlorophylls
Energy Transfer
Chromophores
Pigments
Energy transfer
Cations
Absorption spectra
Bacteria
Zinc
Positive ions
Wavelength
Oxidation

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Multiporphyrin arrays with π-π Interchromophore interactions. / Terazono, Yuichi; Kodis, Gerdenis; Chachisvilis, Mirianas; Cherry, Brian R.; Fournier, Maxime; Moore, Ana L; Moore, Thomas A; Gust, John Devens.

In: Journal of the American Chemical Society, Vol. 137, No. 1, 14.01.2015, p. 245-258.

Research output: Contribution to journalArticle

Terazono Y, Kodis G, Chachisvilis M, Cherry BR, Fournier M, Moore AL et al. Multiporphyrin arrays with π-π Interchromophore interactions. Journal of the American Chemical Society. 2015 Jan 14;137(1):245-258. https://doi.org/10.1021/ja510267c
Terazono, Yuichi ; Kodis, Gerdenis ; Chachisvilis, Mirianas ; Cherry, Brian R. ; Fournier, Maxime ; Moore, Ana L ; Moore, Thomas A ; Gust, John Devens. / Multiporphyrin arrays with π-π Interchromophore interactions. In: Journal of the American Chemical Society. 2015 ; Vol. 137, No. 1. pp. 245-258.
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