A directly fused tetrameric porphyrin sheet and its anomalous electronic properties that arise from the planar cyclooctatetraene core

Yasuyuki Nakamura, Naoki Aratani, Hiroshi Shinokubo, Akihiko Takagi, Tomoji Kawai, Takuya Matsumoto, Zin Seok Yoon, Deok Yun Kim, Tae Kyu Ahn, Dongho Kim, Atsuya Muranaka, Nagao Kobayashi, Atsuhiro Osuka

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Abstract

Oxidation of a directly meso-meso linked cyclic porphyrin tetramer 2 gave a porphyrin sheet 3. The symmetric square structure of 3 is indicated by its simple 1H NMR spectrum that exhibits only two signals for the porphyrin β-protons. The absorption spectrum of 3 displays characteristic Soret-like broad bands and weak Q-bands, and its magnetic circular dichroism (MCD) spectrum exhibits a negative Faraday A term at the 762 nm band as a rare case, indicating the absorption as a transition from a nondegenerate level to a degenerate level. A slightly longer S1-state (1.1 ps) and smaller TPA cross section (2750 GM) than a tetrameric linear porphyrin tape also indicate its unique electronic properties. The porphyrin sheet 3 forms stable 1:2 complexes with guest molecules G1 and G2, whose 1H NMR spectra exhibit remarkable downfield shifts for the guest protons that are located just above the cyclooctatetraene (COT) core of 3, whereas the imidazolyl protons bound to the zinc(II) porphyrin local cores are observed at slightly upfield positions. These results have been qualitatively accounted for in terms of the presence of a strong paratropic ring current around the COT core that propagates through the whole π-electronic network of 3, hence competing with and canceling the weak diatropic ring currents of the local zinc(II) porphyrins. This explanation was supported by DFT calculation performed at the GIAO-B3LYP/6-31G* level, which indicated large positive NICS values within the COT core and small NICS values within the local zinc(II) porphyrins.

Original languageEnglish
Pages (from-to)4119-4127
Number of pages9
JournalJournal of the American Chemical Society
Volume128
Issue number12
DOIs
Publication statusPublished - 2006 Mar 29

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Porphyrins
Electronic properties
Protons
Zinc
Circular Dichroism
Nuclear magnetic resonance
Dichroism
Discrete Fourier transforms
Tapes
Absorption spectra
Display devices
zinc hematoporphyrin
Oxidation
Molecules
Proton Magnetic Resonance Spectroscopy

All Science Journal Classification (ASJC) codes

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

Cite this

Nakamura, Yasuyuki ; Aratani, Naoki ; Shinokubo, Hiroshi ; Takagi, Akihiko ; Kawai, Tomoji ; Matsumoto, Takuya ; Yoon, Zin Seok ; Kim, Deok Yun ; Ahn, Tae Kyu ; Kim, Dongho ; Muranaka, Atsuya ; Kobayashi, Nagao ; Osuka, Atsuhiro. / A directly fused tetrameric porphyrin sheet and its anomalous electronic properties that arise from the planar cyclooctatetraene core. In: Journal of the American Chemical Society. 2006 ; Vol. 128, No. 12. pp. 4119-4127.
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title = "A directly fused tetrameric porphyrin sheet and its anomalous electronic properties that arise from the planar cyclooctatetraene core",
abstract = "Oxidation of a directly meso-meso linked cyclic porphyrin tetramer 2 gave a porphyrin sheet 3. The symmetric square structure of 3 is indicated by its simple 1H NMR spectrum that exhibits only two signals for the porphyrin β-protons. The absorption spectrum of 3 displays characteristic Soret-like broad bands and weak Q-bands, and its magnetic circular dichroism (MCD) spectrum exhibits a negative Faraday A term at the 762 nm band as a rare case, indicating the absorption as a transition from a nondegenerate level to a degenerate level. A slightly longer S1-state (1.1 ps) and smaller TPA cross section (2750 GM) than a tetrameric linear porphyrin tape also indicate its unique electronic properties. The porphyrin sheet 3 forms stable 1:2 complexes with guest molecules G1 and G2, whose 1H NMR spectra exhibit remarkable downfield shifts for the guest protons that are located just above the cyclooctatetraene (COT) core of 3, whereas the imidazolyl protons bound to the zinc(II) porphyrin local cores are observed at slightly upfield positions. These results have been qualitatively accounted for in terms of the presence of a strong paratropic ring current around the COT core that propagates through the whole π-electronic network of 3, hence competing with and canceling the weak diatropic ring currents of the local zinc(II) porphyrins. This explanation was supported by DFT calculation performed at the GIAO-B3LYP/6-31G* level, which indicated large positive NICS values within the COT core and small NICS values within the local zinc(II) porphyrins.",
author = "Yasuyuki Nakamura and Naoki Aratani and Hiroshi Shinokubo and Akihiko Takagi and Tomoji Kawai and Takuya Matsumoto and Yoon, {Zin Seok} and Kim, {Deok Yun} and Ahn, {Tae Kyu} and Dongho Kim and Atsuya Muranaka and Nagao Kobayashi and Atsuhiro Osuka",
year = "2006",
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Nakamura, Y, Aratani, N, Shinokubo, H, Takagi, A, Kawai, T, Matsumoto, T, Yoon, ZS, Kim, DY, Ahn, TK, Kim, D, Muranaka, A, Kobayashi, N & Osuka, A 2006, 'A directly fused tetrameric porphyrin sheet and its anomalous electronic properties that arise from the planar cyclooctatetraene core', Journal of the American Chemical Society, vol. 128, no. 12, pp. 4119-4127. https://doi.org/10.1021/ja057812l

A directly fused tetrameric porphyrin sheet and its anomalous electronic properties that arise from the planar cyclooctatetraene core. / Nakamura, Yasuyuki; Aratani, Naoki; Shinokubo, Hiroshi; Takagi, Akihiko; Kawai, Tomoji; Matsumoto, Takuya; Yoon, Zin Seok; Kim, Deok Yun; Ahn, Tae Kyu; Kim, Dongho; Muranaka, Atsuya; Kobayashi, Nagao; Osuka, Atsuhiro.

In: Journal of the American Chemical Society, Vol. 128, No. 12, 29.03.2006, p. 4119-4127.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A directly fused tetrameric porphyrin sheet and its anomalous electronic properties that arise from the planar cyclooctatetraene core

AU - Nakamura, Yasuyuki

AU - Aratani, Naoki

AU - Shinokubo, Hiroshi

AU - Takagi, Akihiko

AU - Kawai, Tomoji

AU - Matsumoto, Takuya

AU - Yoon, Zin Seok

AU - Kim, Deok Yun

AU - Ahn, Tae Kyu

AU - Kim, Dongho

AU - Muranaka, Atsuya

AU - Kobayashi, Nagao

AU - Osuka, Atsuhiro

PY - 2006/3/29

Y1 - 2006/3/29

N2 - Oxidation of a directly meso-meso linked cyclic porphyrin tetramer 2 gave a porphyrin sheet 3. The symmetric square structure of 3 is indicated by its simple 1H NMR spectrum that exhibits only two signals for the porphyrin β-protons. The absorption spectrum of 3 displays characteristic Soret-like broad bands and weak Q-bands, and its magnetic circular dichroism (MCD) spectrum exhibits a negative Faraday A term at the 762 nm band as a rare case, indicating the absorption as a transition from a nondegenerate level to a degenerate level. A slightly longer S1-state (1.1 ps) and smaller TPA cross section (2750 GM) than a tetrameric linear porphyrin tape also indicate its unique electronic properties. The porphyrin sheet 3 forms stable 1:2 complexes with guest molecules G1 and G2, whose 1H NMR spectra exhibit remarkable downfield shifts for the guest protons that are located just above the cyclooctatetraene (COT) core of 3, whereas the imidazolyl protons bound to the zinc(II) porphyrin local cores are observed at slightly upfield positions. These results have been qualitatively accounted for in terms of the presence of a strong paratropic ring current around the COT core that propagates through the whole π-electronic network of 3, hence competing with and canceling the weak diatropic ring currents of the local zinc(II) porphyrins. This explanation was supported by DFT calculation performed at the GIAO-B3LYP/6-31G* level, which indicated large positive NICS values within the COT core and small NICS values within the local zinc(II) porphyrins.

AB - Oxidation of a directly meso-meso linked cyclic porphyrin tetramer 2 gave a porphyrin sheet 3. The symmetric square structure of 3 is indicated by its simple 1H NMR spectrum that exhibits only two signals for the porphyrin β-protons. The absorption spectrum of 3 displays characteristic Soret-like broad bands and weak Q-bands, and its magnetic circular dichroism (MCD) spectrum exhibits a negative Faraday A term at the 762 nm band as a rare case, indicating the absorption as a transition from a nondegenerate level to a degenerate level. A slightly longer S1-state (1.1 ps) and smaller TPA cross section (2750 GM) than a tetrameric linear porphyrin tape also indicate its unique electronic properties. The porphyrin sheet 3 forms stable 1:2 complexes with guest molecules G1 and G2, whose 1H NMR spectra exhibit remarkable downfield shifts for the guest protons that are located just above the cyclooctatetraene (COT) core of 3, whereas the imidazolyl protons bound to the zinc(II) porphyrin local cores are observed at slightly upfield positions. These results have been qualitatively accounted for in terms of the presence of a strong paratropic ring current around the COT core that propagates through the whole π-electronic network of 3, hence competing with and canceling the weak diatropic ring currents of the local zinc(II) porphyrins. This explanation was supported by DFT calculation performed at the GIAO-B3LYP/6-31G* level, which indicated large positive NICS values within the COT core and small NICS values within the local zinc(II) porphyrins.

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