Directly meso-meso linked porphyrin rings

Synthesis, characterization, and efficient excitation energy hopping

Yasuyuki Nakamura, In Wook Hwang, Naoki Aratani, Tae Kyu Ahn, Dah Mee Ko, Akihiko Takagi, Tomoji Kawai, Takuya Matsumoto, Dongho Kim, Atsuhiro Osuka

Research output: Contribution to journalArticle

136 Citations (Scopus)

Abstract

Directly meso-meso linked porphyrin rings CZ4, CZ6, and CZ8 that respectively comprise four, six, and eight porphyrins have been synthesized in a stepwise manner from a 5, 10-diaryl zinc(II) porphyrin building block. Symmetric cyclic structures have been indicated by their very simple 1H NMR spectra that exhibit only a single set of porphyrin and their absorption spectra that display a characteristic broad nonsplit Soret band around 460 nm. Energy minimized structures calculated at the B3LYP/6-31G* level indicate that a dihedral angle between neighboring porphyrins decreases in order of CZ6 > CZ8 > CZ4, which is consistent with the 1H NMR data. Photophysical properties of these molecules have been examined by the steady-state absorption, fluorescence, fluorescence lifetime, fluorescence anisotropy decay, and transient absorption measurements. Both the pump-power dependence on the femtosecond transient absorption and the transient absorption anisotropy decay profiles are directly related with the excitation energy migration processes within the porphyrin rings, where the exciton-exciton annihilation time and the polarization anisotropy rise time are well described in terms of the Förster-type incoherent energy hopping model. Consequently, the excitation energy hopping rates have been estimated for CZ4 (119 ± 2 fs)-1, CZ6 (342 ± 59 fs)-1, and CZ8 (236 ± 31 fs)-1, which reflect the magnitude of the electronic coupling between the neighboring porphyrins. Overall, these porphyrin rings serve as a well-defined wheel-shaped light harvesting antenna model in light of very efficient excitation energy hopping along the ring.

Original languageEnglish
Pages (from-to)236-246
Number of pages11
JournalJournal of the American Chemical Society
Volume127
Issue number1
DOIs
Publication statusPublished - 2005 Jan 12

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Excitation energy
Porphyrins
Anisotropy
Fluorescence
Excitons
Nuclear magnetic resonance
Fluorescence Polarization
Dihedral angle
Zinc
Absorption spectra
Wheels
Light
Pumps
Polarization
Antennas
Molecules

All Science Journal Classification (ASJC) codes

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

Cite this

Nakamura, Yasuyuki ; Hwang, In Wook ; Aratani, Naoki ; Ahn, Tae Kyu ; Ko, Dah Mee ; Takagi, Akihiko ; Kawai, Tomoji ; Matsumoto, Takuya ; Kim, Dongho ; Osuka, Atsuhiro. / Directly meso-meso linked porphyrin rings : Synthesis, characterization, and efficient excitation energy hopping. In: Journal of the American Chemical Society. 2005 ; Vol. 127, No. 1. pp. 236-246.
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title = "Directly meso-meso linked porphyrin rings: Synthesis, characterization, and efficient excitation energy hopping",
abstract = "Directly meso-meso linked porphyrin rings CZ4, CZ6, and CZ8 that respectively comprise four, six, and eight porphyrins have been synthesized in a stepwise manner from a 5, 10-diaryl zinc(II) porphyrin building block. Symmetric cyclic structures have been indicated by their very simple 1H NMR spectra that exhibit only a single set of porphyrin and their absorption spectra that display a characteristic broad nonsplit Soret band around 460 nm. Energy minimized structures calculated at the B3LYP/6-31G* level indicate that a dihedral angle between neighboring porphyrins decreases in order of CZ6 > CZ8 > CZ4, which is consistent with the 1H NMR data. Photophysical properties of these molecules have been examined by the steady-state absorption, fluorescence, fluorescence lifetime, fluorescence anisotropy decay, and transient absorption measurements. Both the pump-power dependence on the femtosecond transient absorption and the transient absorption anisotropy decay profiles are directly related with the excitation energy migration processes within the porphyrin rings, where the exciton-exciton annihilation time and the polarization anisotropy rise time are well described in terms of the F{\"o}rster-type incoherent energy hopping model. Consequently, the excitation energy hopping rates have been estimated for CZ4 (119 ± 2 fs)-1, CZ6 (342 ± 59 fs)-1, and CZ8 (236 ± 31 fs)-1, which reflect the magnitude of the electronic coupling between the neighboring porphyrins. Overall, these porphyrin rings serve as a well-defined wheel-shaped light harvesting antenna model in light of very efficient excitation energy hopping along the ring.",
author = "Yasuyuki Nakamura and Hwang, {In Wook} and Naoki Aratani and Ahn, {Tae Kyu} and Ko, {Dah Mee} and Akihiko Takagi and Tomoji Kawai and Takuya Matsumoto and Dongho Kim and Atsuhiro Osuka",
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Nakamura, Y, Hwang, IW, Aratani, N, Ahn, TK, Ko, DM, Takagi, A, Kawai, T, Matsumoto, T, Kim, D & Osuka, A 2005, 'Directly meso-meso linked porphyrin rings: Synthesis, characterization, and efficient excitation energy hopping', Journal of the American Chemical Society, vol. 127, no. 1, pp. 236-246. https://doi.org/10.1021/ja045254p

Directly meso-meso linked porphyrin rings : Synthesis, characterization, and efficient excitation energy hopping. / Nakamura, Yasuyuki; Hwang, In Wook; Aratani, Naoki; Ahn, Tae Kyu; Ko, Dah Mee; Takagi, Akihiko; Kawai, Tomoji; Matsumoto, Takuya; Kim, Dongho; Osuka, Atsuhiro.

In: Journal of the American Chemical Society, Vol. 127, No. 1, 12.01.2005, p. 236-246.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Directly meso-meso linked porphyrin rings

T2 - Synthesis, characterization, and efficient excitation energy hopping

AU - Nakamura, Yasuyuki

AU - Hwang, In Wook

AU - Aratani, Naoki

AU - Ahn, Tae Kyu

AU - Ko, Dah Mee

AU - Takagi, Akihiko

AU - Kawai, Tomoji

AU - Matsumoto, Takuya

AU - Kim, Dongho

AU - Osuka, Atsuhiro

PY - 2005/1/12

Y1 - 2005/1/12

N2 - Directly meso-meso linked porphyrin rings CZ4, CZ6, and CZ8 that respectively comprise four, six, and eight porphyrins have been synthesized in a stepwise manner from a 5, 10-diaryl zinc(II) porphyrin building block. Symmetric cyclic structures have been indicated by their very simple 1H NMR spectra that exhibit only a single set of porphyrin and their absorption spectra that display a characteristic broad nonsplit Soret band around 460 nm. Energy minimized structures calculated at the B3LYP/6-31G* level indicate that a dihedral angle between neighboring porphyrins decreases in order of CZ6 > CZ8 > CZ4, which is consistent with the 1H NMR data. Photophysical properties of these molecules have been examined by the steady-state absorption, fluorescence, fluorescence lifetime, fluorescence anisotropy decay, and transient absorption measurements. Both the pump-power dependence on the femtosecond transient absorption and the transient absorption anisotropy decay profiles are directly related with the excitation energy migration processes within the porphyrin rings, where the exciton-exciton annihilation time and the polarization anisotropy rise time are well described in terms of the Förster-type incoherent energy hopping model. Consequently, the excitation energy hopping rates have been estimated for CZ4 (119 ± 2 fs)-1, CZ6 (342 ± 59 fs)-1, and CZ8 (236 ± 31 fs)-1, which reflect the magnitude of the electronic coupling between the neighboring porphyrins. Overall, these porphyrin rings serve as a well-defined wheel-shaped light harvesting antenna model in light of very efficient excitation energy hopping along the ring.

AB - Directly meso-meso linked porphyrin rings CZ4, CZ6, and CZ8 that respectively comprise four, six, and eight porphyrins have been synthesized in a stepwise manner from a 5, 10-diaryl zinc(II) porphyrin building block. Symmetric cyclic structures have been indicated by their very simple 1H NMR spectra that exhibit only a single set of porphyrin and their absorption spectra that display a characteristic broad nonsplit Soret band around 460 nm. Energy minimized structures calculated at the B3LYP/6-31G* level indicate that a dihedral angle between neighboring porphyrins decreases in order of CZ6 > CZ8 > CZ4, which is consistent with the 1H NMR data. Photophysical properties of these molecules have been examined by the steady-state absorption, fluorescence, fluorescence lifetime, fluorescence anisotropy decay, and transient absorption measurements. Both the pump-power dependence on the femtosecond transient absorption and the transient absorption anisotropy decay profiles are directly related with the excitation energy migration processes within the porphyrin rings, where the exciton-exciton annihilation time and the polarization anisotropy rise time are well described in terms of the Förster-type incoherent energy hopping model. Consequently, the excitation energy hopping rates have been estimated for CZ4 (119 ± 2 fs)-1, CZ6 (342 ± 59 fs)-1, and CZ8 (236 ± 31 fs)-1, which reflect the magnitude of the electronic coupling between the neighboring porphyrins. Overall, these porphyrin rings serve as a well-defined wheel-shaped light harvesting antenna model in light of very efficient excitation energy hopping along the ring.

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U2 - 10.1021/ja045254p

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