The First Silicon(IV) Corrole Complexes

Synthesis, Structures, Properties, and Formation of a μ-Oxo Dimer

Kento Ueta, Masaya Fukuda, Gakhyun Kim, Soji Shimizu, Takayuki Tanaka, Dongho Kim, Atsuhiro Osuka

研究成果: ジャーナルへの寄稿記事

4 引用 (Scopus)

抄録

The first SiIV corrole complexes were synthesized in good yields by treatment of meso-triarylcorroles with tetrachlorosilane in 1,2-dichloroethane at 60 °C. The central silicon atom possesses a square-pyramidal coordination geometry with slightly longer Si−N bond lengths as compared with those of known triazacorrole SiIV complexes. The SiIV corrole complexes exhibit sharp and blue-shifted absorption spectra and larger fluorescence quantum yields as compared with the corresponding free-base corroles. A μ-oxo dimer of a SiIV corrole was synthesized upon treatment with methanesulfonyl chloride in pyridine at 100 °C. This dimer shows a face-to-face structure with a 90° twist in the solid state. Although the dimer exhibits a blue-shifted Soret band, reflecting the face-to-face geometry, it displays a largely red-shifted and broad fluorescence spectrum with a large Stokes shift, suggesting a large structural change in the S1 state. These intriguing optical properties have been comprehensively studied by magnetic circular dichroism (MCD) spectroscopy, femtosecond transient absorption (fs-TA) measurements, and theoretical calculations.

元の言語英語
ページ(範囲)7637-7646
ページ数10
ジャーナルChemistry - A European Journal
24
発行部数30
DOI
出版物ステータス出版済み - 5 28 2018

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Silicon
Dimers
Fluorescence
Circular dichroism spectroscopy
Geometry
Bond length
Quantum yield
Pyridine
Absorption spectra
Optical properties
Atoms
corrole

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

これを引用

The First Silicon(IV) Corrole Complexes : Synthesis, Structures, Properties, and Formation of a μ-Oxo Dimer. / Ueta, Kento; Fukuda, Masaya; Kim, Gakhyun; Shimizu, Soji; Tanaka, Takayuki; Kim, Dongho; Osuka, Atsuhiro.

:: Chemistry - A European Journal, 巻 24, 番号 30, 28.05.2018, p. 7637-7646.

研究成果: ジャーナルへの寄稿記事

Ueta, Kento ; Fukuda, Masaya ; Kim, Gakhyun ; Shimizu, Soji ; Tanaka, Takayuki ; Kim, Dongho ; Osuka, Atsuhiro. / The First Silicon(IV) Corrole Complexes : Synthesis, Structures, Properties, and Formation of a μ-Oxo Dimer. :: Chemistry - A European Journal. 2018 ; 巻 24, 番号 30. pp. 7637-7646.
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abstract = "The first SiIV corrole complexes were synthesized in good yields by treatment of meso-triarylcorroles with tetrachlorosilane in 1,2-dichloroethane at 60 °C. The central silicon atom possesses a square-pyramidal coordination geometry with slightly longer Si−N bond lengths as compared with those of known triazacorrole SiIV complexes. The SiIV corrole complexes exhibit sharp and blue-shifted absorption spectra and larger fluorescence quantum yields as compared with the corresponding free-base corroles. A μ-oxo dimer of a SiIV corrole was synthesized upon treatment with methanesulfonyl chloride in pyridine at 100 °C. This dimer shows a face-to-face structure with a 90° twist in the solid state. Although the dimer exhibits a blue-shifted Soret band, reflecting the face-to-face geometry, it displays a largely red-shifted and broad fluorescence spectrum with a large Stokes shift, suggesting a large structural change in the S1 state. These intriguing optical properties have been comprehensively studied by magnetic circular dichroism (MCD) spectroscopy, femtosecond transient absorption (fs-TA) measurements, and theoretical calculations.",
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