Synthesis, optical properties, and electronic structures of fully core-modified porphyrin dications and isophlorins

Masaru Kon-No, John MacK, Nagao Kobayashi, Masahiko Suenaga, Kenji Yoza, Teruo Shinmyozu

研究成果: ジャーナルへの寄稿記事

22 引用 (Scopus)

抄録

The synthesis, structures, optical properties, and electronic structures of the tetraphenyltetrathiaporphyrin dication (S 4TPP 2+, 6) and tetrakis(pentafluorophenyl)tetrathiaisophlorin (S 4F 20TPP, 7) are reported. S 4TPP 2+ (6) and S 4F 20TPP (7) were synthesized by acid-catalyzed condensation of the corresponding hydroxylmethylthiophene, followed by oxidation. The electronic structures of S 4TPP 2+ (6) and S 4F 20TPP (7) were analyzed by using UV/Vis-absorption spectroscopy and by magnetic /ular dichroism (MCD) spectroscopy and the bands were assigned by using time-dependent density functional theory (TD-DFT) and ZINDO/s calculations. A red-shift of the Q bands of S 4TPP 2+ (6) is observed relative to the spectra of tetraphenylporphyrins because a destabilization of the HOMO leads to a narrower HOMO-LUMO band-gap. Michl's perimeter model was used to assign the absorption bands and MCD spectra of S 4F 20TPP (7). Current-density maps and nucleus-independent chemical-shift (NICS) calculations of S 4TPP 2+ (6) and of a model compound predict marked modification to the diamagnetic ring current, whilst nonaromatic character is predicted for S 4F 20TPP (7).

元の言語英語
ページ(範囲)13361-13371
ページ数11
ジャーナルChemistry - A European Journal
18
発行部数42
DOI
出版物ステータス出版済み - 10 15 2012

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Porphyrins
Dichroism
Electronic structure
Optical properties
Chemical shift
Ultraviolet spectroscopy
Absorption spectroscopy
Density functional theory
Absorption spectra
Condensation
Energy gap
Current density
Spectroscopy
Oxidation
Acids
tetraphenylporphyrin

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

これを引用

Synthesis, optical properties, and electronic structures of fully core-modified porphyrin dications and isophlorins. / Kon-No, Masaru; MacK, John; Kobayashi, Nagao; Suenaga, Masahiko; Yoza, Kenji; Shinmyozu, Teruo.

:: Chemistry - A European Journal, 巻 18, 番号 42, 15.10.2012, p. 13361-13371.

研究成果: ジャーナルへの寄稿記事

Kon-No, Masaru ; MacK, John ; Kobayashi, Nagao ; Suenaga, Masahiko ; Yoza, Kenji ; Shinmyozu, Teruo. / Synthesis, optical properties, and electronic structures of fully core-modified porphyrin dications and isophlorins. :: Chemistry - A European Journal. 2012 ; 巻 18, 番号 42. pp. 13361-13371.
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abstract = "The synthesis, structures, optical properties, and electronic structures of the tetraphenyltetrathiaporphyrin dication (S 4TPP 2+, 6) and tetrakis(pentafluorophenyl)tetrathiaisophlorin (S 4F 20TPP, 7) are reported. S 4TPP 2+ (6) and S 4F 20TPP (7) were synthesized by acid-catalyzed condensation of the corresponding hydroxylmethylthiophene, followed by oxidation. The electronic structures of S 4TPP 2+ (6) and S 4F 20TPP (7) were analyzed by using UV/Vis-absorption spectroscopy and by magnetic /ular dichroism (MCD) spectroscopy and the bands were assigned by using time-dependent density functional theory (TD-DFT) and ZINDO/s calculations. A red-shift of the Q bands of S 4TPP 2+ (6) is observed relative to the spectra of tetraphenylporphyrins because a destabilization of the HOMO leads to a narrower HOMO-LUMO band-gap. Michl's perimeter model was used to assign the absorption bands and MCD spectra of S 4F 20TPP (7). Current-density maps and nucleus-independent chemical-shift (NICS) calculations of S 4TPP 2+ (6) and of a model compound predict marked modification to the diamagnetic ring current, whilst nonaromatic character is predicted for S 4F 20TPP (7).",
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AU - MacK, John

AU - Kobayashi, Nagao

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AU - Yoza, Kenji

AU - Shinmyozu, Teruo

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AB - The synthesis, structures, optical properties, and electronic structures of the tetraphenyltetrathiaporphyrin dication (S 4TPP 2+, 6) and tetrakis(pentafluorophenyl)tetrathiaisophlorin (S 4F 20TPP, 7) are reported. S 4TPP 2+ (6) and S 4F 20TPP (7) were synthesized by acid-catalyzed condensation of the corresponding hydroxylmethylthiophene, followed by oxidation. The electronic structures of S 4TPP 2+ (6) and S 4F 20TPP (7) were analyzed by using UV/Vis-absorption spectroscopy and by magnetic /ular dichroism (MCD) spectroscopy and the bands were assigned by using time-dependent density functional theory (TD-DFT) and ZINDO/s calculations. A red-shift of the Q bands of S 4TPP 2+ (6) is observed relative to the spectra of tetraphenylporphyrins because a destabilization of the HOMO leads to a narrower HOMO-LUMO band-gap. Michl's perimeter model was used to assign the absorption bands and MCD spectra of S 4F 20TPP (7). Current-density maps and nucleus-independent chemical-shift (NICS) calculations of S 4TPP 2+ (6) and of a model compound predict marked modification to the diamagnetic ring current, whilst nonaromatic character is predicted for S 4F 20TPP (7).

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