Synthesis and Photophysical Properties of Two Diazaporphyrin-Porphyrin Hetero Dimers in Polar and Nonpolar Solutions

Fawzi Abou-Chahine, Daisuke Fujii, Hiroshi Imahori, Haruyuki Nakano, Nikolai V. Tkachenko, Yoshihiro Matano, Helge Lemmetyinen

Research output: Contribution to journalArticle

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Abstract

Two diazaporphyrin (DAP)-porphyrin hetero dimers, in β-meso and β-β configurations, were prepared to study their photoinduced intramolecular electron transfer properties. The two meso nitrogen atoms in the porphyrin ring of DAP change its redox potential, making DAP more easily reduced, compared to its porphyrin counterpart. A charge-transfer from porphyrin to DAP in both hetero dimers was verified by versatile optical spectroscopic methods. The steady-state fluorescence spectra indicated an efficient intramolecular exciplex formation for both dimers. For the β-meso dimer, ultrafast time-resolved spectroscopic methods revealed the subpicosecond formation of two types of primary short-living (1-18 ps) intramolecular exciplexes, which relaxed in toluene to form a long-living final exciplex (1.4 ns) followed by a longer-living charge transfer complex (>5 ns). However, in benzonitrile, the lifetime of the final exciplex was longer (660 ps) as was that of the charge transfer complex (180 ps). The β-β analogue formed similar short-living exciplexes in both solvents, but the final exciplex and the charge transfer state had significantly shorter lifetimes. The electrochemical redox potential measurements and density functional theory calculations supported the proposed mechanism.

Original languageEnglish
Pages (from-to)7328-7337
Number of pages10
JournalJournal of Physical Chemistry B
Volume119
Issue number24
DOIs
Publication statusPublished - Jun 18 2015

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Porphyrins
porphyrins
Dimers
Charge transfer
dimers
charge transfer
synthesis
Oxidation-Reduction
life (durability)
Toluene
nitrogen atoms
Density functional theory
toluene
electron transfer
Nitrogen
Fluorescence
Electrons
analogs
density functional theory
Atoms

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Synthesis and Photophysical Properties of Two Diazaporphyrin-Porphyrin Hetero Dimers in Polar and Nonpolar Solutions. / Abou-Chahine, Fawzi; Fujii, Daisuke; Imahori, Hiroshi; Nakano, Haruyuki; Tkachenko, Nikolai V.; Matano, Yoshihiro; Lemmetyinen, Helge.

In: Journal of Physical Chemistry B, Vol. 119, No. 24, 18.06.2015, p. 7328-7337.

Research output: Contribution to journalArticle

Abou-Chahine, Fawzi ; Fujii, Daisuke ; Imahori, Hiroshi ; Nakano, Haruyuki ; Tkachenko, Nikolai V. ; Matano, Yoshihiro ; Lemmetyinen, Helge. / Synthesis and Photophysical Properties of Two Diazaporphyrin-Porphyrin Hetero Dimers in Polar and Nonpolar Solutions. In: Journal of Physical Chemistry B. 2015 ; Vol. 119, No. 24. pp. 7328-7337.
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