Giant porphyrin wheels with large electronic coupling as models of light-harvesting photosynthetic antenna

Takaaki Hori, Naoki Aratani, Akihiko Takagi, Takuya Matsumoto, Tomoji Kawai, Min Chul Yoon, Zin Seok Yoon, Sung Cho, Kim Dongho, Atsuhiro Osuka

Research output: Contribution to journalArticle

84 Citations (Scopus)

Abstract

Starting from a 1,3-phenylene-linked diporphyrin zinc(II) complex 2ZA, repeated stepwise AgI-promoted coupling reactions provided linear oligomers 4ZA, 6ZA, 8ZA, and 12ZA. The intramolecular cyclization reaction of 12ZA under dilute conditions (1 × 10-6 M) gave porphyrin ring C12ZA with a diameter of approximately 35 Å in 60% yield. This synthetic strategy has been applied to a 1,3-pnenylene-linked tetraporphyrin 4ZB to provide 8ZB, 12ZB, 16ZB, 24ZB, and 32ZB. The intramolecular coupling reaction of 24ZB gave a larger 24-mer porphyrin ring C24ZB with a diameter of approximately 70 Å in 34% yield. These two large porphyrin rings were characterized by means of 1H NMR spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDITOF) mass spectroscopy, UV-visible spectroscopy, gel permeation chromatography (GPC) analysis, and scanning tunneling microscopy (STM) techniques. The STM images of C12ZA reveal largely circular structures, whereas those of C24ZB exhibit mostly ellipsoidal shapes, indicating more con formational flexibility of C24ZB. Similar to the case of C12ZA, the efficient excitation energy transfer along the ring has been confirmed for C24ZB by using the time-correlated single-photon counting (TCSPC) and picosecond transient absorption anisotropy (TAA) measurements, and occurs with a rate of (35 ps) -1 for energy hops between neighboring tetraporphyrin subunits. Collectively, the present work provides an important step for the construction of large cyclic-arranged porphyrin arrays with ample electronic interactions as a model of light-harvesting antenna.

Original languageEnglish
Pages (from-to)1319-1327
Number of pages9
JournalChemistry - A European Journal
Volume12
Issue number5
DOIs
Publication statusPublished - 2006 Feb 1

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Porphyrins
Wheels
Antennas
Scanning tunneling microscopy
Excitation energy
Cyclization
Gel permeation chromatography
Ultraviolet spectroscopy
Oligomers
Energy transfer
Nuclear magnetic resonance spectroscopy
Ionization
Zinc
Desorption
Anisotropy
Photons
Spectroscopy
Lasers

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Hori, T., Aratani, N., Takagi, A., Matsumoto, T., Kawai, T., Yoon, M. C., ... Osuka, A. (2006). Giant porphyrin wheels with large electronic coupling as models of light-harvesting photosynthetic antenna. Chemistry - A European Journal, 12(5), 1319-1327. https://doi.org/10.1002/chem.200501373
Hori, Takaaki ; Aratani, Naoki ; Takagi, Akihiko ; Matsumoto, Takuya ; Kawai, Tomoji ; Yoon, Min Chul ; Yoon, Zin Seok ; Cho, Sung ; Dongho, Kim ; Osuka, Atsuhiro. / Giant porphyrin wheels with large electronic coupling as models of light-harvesting photosynthetic antenna. In: Chemistry - A European Journal. 2006 ; Vol. 12, No. 5. pp. 1319-1327.
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abstract = "Starting from a 1,3-phenylene-linked diporphyrin zinc(II) complex 2ZA, repeated stepwise AgI-promoted coupling reactions provided linear oligomers 4ZA, 6ZA, 8ZA, and 12ZA. The intramolecular cyclization reaction of 12ZA under dilute conditions (1 × 10-6 M) gave porphyrin ring C12ZA with a diameter of approximately 35 {\AA} in 60{\%} yield. This synthetic strategy has been applied to a 1,3-pnenylene-linked tetraporphyrin 4ZB to provide 8ZB, 12ZB, 16ZB, 24ZB, and 32ZB. The intramolecular coupling reaction of 24ZB gave a larger 24-mer porphyrin ring C24ZB with a diameter of approximately 70 {\AA} in 34{\%} yield. These two large porphyrin rings were characterized by means of 1H NMR spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDITOF) mass spectroscopy, UV-visible spectroscopy, gel permeation chromatography (GPC) analysis, and scanning tunneling microscopy (STM) techniques. The STM images of C12ZA reveal largely circular structures, whereas those of C24ZB exhibit mostly ellipsoidal shapes, indicating more con formational flexibility of C24ZB. Similar to the case of C12ZA, the efficient excitation energy transfer along the ring has been confirmed for C24ZB by using the time-correlated single-photon counting (TCSPC) and picosecond transient absorption anisotropy (TAA) measurements, and occurs with a rate of (35 ps) -1 for energy hops between neighboring tetraporphyrin subunits. Collectively, the present work provides an important step for the construction of large cyclic-arranged porphyrin arrays with ample electronic interactions as a model of light-harvesting antenna.",
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Hori, T, Aratani, N, Takagi, A, Matsumoto, T, Kawai, T, Yoon, MC, Yoon, ZS, Cho, S, Dongho, K & Osuka, A 2006, 'Giant porphyrin wheels with large electronic coupling as models of light-harvesting photosynthetic antenna', Chemistry - A European Journal, vol. 12, no. 5, pp. 1319-1327. https://doi.org/10.1002/chem.200501373

Giant porphyrin wheels with large electronic coupling as models of light-harvesting photosynthetic antenna. / Hori, Takaaki; Aratani, Naoki; Takagi, Akihiko; Matsumoto, Takuya; Kawai, Tomoji; Yoon, Min Chul; Yoon, Zin Seok; Cho, Sung; Dongho, Kim; Osuka, Atsuhiro.

In: Chemistry - A European Journal, Vol. 12, No. 5, 01.02.2006, p. 1319-1327.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Giant porphyrin wheels with large electronic coupling as models of light-harvesting photosynthetic antenna

AU - Hori, Takaaki

AU - Aratani, Naoki

AU - Takagi, Akihiko

AU - Matsumoto, Takuya

AU - Kawai, Tomoji

AU - Yoon, Min Chul

AU - Yoon, Zin Seok

AU - Cho, Sung

AU - Dongho, Kim

AU - Osuka, Atsuhiro

PY - 2006/2/1

Y1 - 2006/2/1

N2 - Starting from a 1,3-phenylene-linked diporphyrin zinc(II) complex 2ZA, repeated stepwise AgI-promoted coupling reactions provided linear oligomers 4ZA, 6ZA, 8ZA, and 12ZA. The intramolecular cyclization reaction of 12ZA under dilute conditions (1 × 10-6 M) gave porphyrin ring C12ZA with a diameter of approximately 35 Å in 60% yield. This synthetic strategy has been applied to a 1,3-pnenylene-linked tetraporphyrin 4ZB to provide 8ZB, 12ZB, 16ZB, 24ZB, and 32ZB. The intramolecular coupling reaction of 24ZB gave a larger 24-mer porphyrin ring C24ZB with a diameter of approximately 70 Å in 34% yield. These two large porphyrin rings were characterized by means of 1H NMR spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDITOF) mass spectroscopy, UV-visible spectroscopy, gel permeation chromatography (GPC) analysis, and scanning tunneling microscopy (STM) techniques. The STM images of C12ZA reveal largely circular structures, whereas those of C24ZB exhibit mostly ellipsoidal shapes, indicating more con formational flexibility of C24ZB. Similar to the case of C12ZA, the efficient excitation energy transfer along the ring has been confirmed for C24ZB by using the time-correlated single-photon counting (TCSPC) and picosecond transient absorption anisotropy (TAA) measurements, and occurs with a rate of (35 ps) -1 for energy hops between neighboring tetraporphyrin subunits. Collectively, the present work provides an important step for the construction of large cyclic-arranged porphyrin arrays with ample electronic interactions as a model of light-harvesting antenna.

AB - Starting from a 1,3-phenylene-linked diporphyrin zinc(II) complex 2ZA, repeated stepwise AgI-promoted coupling reactions provided linear oligomers 4ZA, 6ZA, 8ZA, and 12ZA. The intramolecular cyclization reaction of 12ZA under dilute conditions (1 × 10-6 M) gave porphyrin ring C12ZA with a diameter of approximately 35 Å in 60% yield. This synthetic strategy has been applied to a 1,3-pnenylene-linked tetraporphyrin 4ZB to provide 8ZB, 12ZB, 16ZB, 24ZB, and 32ZB. The intramolecular coupling reaction of 24ZB gave a larger 24-mer porphyrin ring C24ZB with a diameter of approximately 70 Å in 34% yield. These two large porphyrin rings were characterized by means of 1H NMR spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDITOF) mass spectroscopy, UV-visible spectroscopy, gel permeation chromatography (GPC) analysis, and scanning tunneling microscopy (STM) techniques. The STM images of C12ZA reveal largely circular structures, whereas those of C24ZB exhibit mostly ellipsoidal shapes, indicating more con formational flexibility of C24ZB. Similar to the case of C12ZA, the efficient excitation energy transfer along the ring has been confirmed for C24ZB by using the time-correlated single-photon counting (TCSPC) and picosecond transient absorption anisotropy (TAA) measurements, and occurs with a rate of (35 ps) -1 for energy hops between neighboring tetraporphyrin subunits. Collectively, the present work provides an important step for the construction of large cyclic-arranged porphyrin arrays with ample electronic interactions as a model of light-harvesting antenna.

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