Structural factors determining photophysical properties of directly linked zinc(II) porphyrin dimers: Linking position, dihedral angle, and linkage length

Sung Cho, Min Chul Yoon, Jong Min Lim, Pyosang Kim, Naoki Aratani, Yasuyuki Nakamura, Toshiaki Ikeda, Atsuhiro Osuka, Dongho Kim*

*Corresponding author for this work

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

We have investigated the relationship between the photophysical properties and structures of a series of directly linked zinc(II) porphyrin dimers (mmZ2, mbZ2, and bbZ2) using time-resolved spectroscopic measurements and theoretical calculations. Their unique characters such as CT nature and torsional motion are caused by interporphyrin interactions and steric effects, respectively, which can be fully understood in terms of three structural factors: linking position, dihedral angle, and linkage length. The orthogonal geometry and heterolinking of mmZ2 and mbZ2 induce the localized MOs and electron unbalance in the constituent porphyrin units, respectively, and consequently lead to distinct CT characters in spite of their different origin. On the other hand, a small interporphyrin steric hindrance in bbZ2 makes a torsional motion possible around the direct β-β′ linkage in the excited state, which is correlated with the solvent dependence of the fast S1fluorescence decay component. On the basis of this work, we can gain further insight into the effect of individual structural factors on the photophysical properties, which provides a firm basis for further understanding of the photophysical properties mainly determined by the structural factors in multiporphyrin systems.

Original languageEnglish (US)
Pages (from-to)10619-10627
Number of pages9
JournalJournal of Physical Chemistry B
Volume113
Issue number31
DOIs
StatePublished - Aug 6 2009

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Porphyrins
Dihedral angle
linkages
porphyrins
Dimers
dihedral angle
Zinc
zinc
dimers
Excited states
Electrons
Geometry
decay
geometry
excitation
zinc hematoporphyrin
electrons
interactions

ASJC Scopus subject areas

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

Cite this

Cho, Sung ; Yoon, Min Chul ; Lim, Jong Min ; Kim, Pyosang ; Aratani, Naoki ; Nakamura, Yasuyuki ; Ikeda, Toshiaki ; Osuka, Atsuhiro ; Kim, Dongho. / Structural factors determining photophysical properties of directly linked zinc(II) porphyrin dimers : Linking position, dihedral angle, and linkage length. In: Journal of Physical Chemistry B. 2009 ; Vol. 113, No. 31. pp. 10619-10627.
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Structural factors determining photophysical properties of directly linked zinc(II) porphyrin dimers : Linking position, dihedral angle, and linkage length. / Cho, Sung; Yoon, Min Chul; Lim, Jong Min; Kim, Pyosang; Aratani, Naoki; Nakamura, Yasuyuki; Ikeda, Toshiaki; Osuka, Atsuhiro; Kim, Dongho.

In: Journal of Physical Chemistry B, Vol. 113, No. 31, 06.08.2009, p. 10619-10627.

Research output: Contribution to journalArticle

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T1 - Structural factors determining photophysical properties of directly linked zinc(II) porphyrin dimers

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AU - Cho, Sung

AU - Yoon, Min Chul

AU - Lim, Jong Min

AU - Kim, Pyosang

AU - Aratani, Naoki

AU - Nakamura, Yasuyuki

AU - Ikeda, Toshiaki

AU - Osuka, Atsuhiro

AU - Kim, Dongho

PY - 2009/8/6

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N2 - We have investigated the relationship between the photophysical properties and structures of a series of directly linked zinc(II) porphyrin dimers (mmZ2, mbZ2, and bbZ2) using time-resolved spectroscopic measurements and theoretical calculations. Their unique characters such as CT nature and torsional motion are caused by interporphyrin interactions and steric effects, respectively, which can be fully understood in terms of three structural factors: linking position, dihedral angle, and linkage length. The orthogonal geometry and heterolinking of mmZ2 and mbZ2 induce the localized MOs and electron unbalance in the constituent porphyrin units, respectively, and consequently lead to distinct CT characters in spite of their different origin. On the other hand, a small interporphyrin steric hindrance in bbZ2 makes a torsional motion possible around the direct β-β′ linkage in the excited state, which is correlated with the solvent dependence of the fast S1fluorescence decay component. On the basis of this work, we can gain further insight into the effect of individual structural factors on the photophysical properties, which provides a firm basis for further understanding of the photophysical properties mainly determined by the structural factors in multiporphyrin systems.

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