Synthesis and properties of redox-switchable zinc complexes of 10,15,20-triaryl-15-aza-5-oxaporphyrin

Keisuke Sudoh, Ko Furukawa, Haruyuki Nakano, Soji Shimizu, Yoshihiro Matano

研究成果: ジャーナルへの寄稿記事

1 引用 (Scopus)

抄録

The synthesis, aromaticity, and optical and electrochemical properties of zinc(II) complexes of 10,15,20-triaryl-15-aza-5-oxaporphyrin (TriAAOP) were investigated. Metal-templated cyclization of a zinc(II) 1,19-dichloro-5,10,15-triaryl-10-azatetrapyrrin complex with an oxygen source afforded 20π TriAAOP in the neutral form. Oxidation of 20π TriAAOP with silver (I) hexafluorophosphate generated the 19π radical cation or 18π dication depending on the content of oxidant used. The interconversion between the three oxidation states (18π, 19π, and 20π) resulted in distinct changes in the aromaticity and optical properties of the 15-aza-5-oxaporphyrin π-system. Nuclear magnetic resonance spectroscopy of 20π TriAAOP revealed its antiaromatic character, whereas that of the 18π TriAAOP dication showed its aromatic character. The combined effect of the two meso-heteroatoms was directly reflected in the redox properties of the porphyrin ring; TriAAOP was reduced more easily and more difficult to oxidize than the zinc(II) complex of 5,10,15,20-tetraaryl-5,15-diaz-aporphyrin (TADAP). In the ultraviolet-visible-near–infrared spectra of the materials, the lowest-energy electronic excitations of the 19π and 18π TriAAOP derivatives were considerably red-shifted compared with those of the isoelectronic TADAP derivatives. Based on the results of density functional theory calculations, it was concluded that the observed differences between TriAAOP and TADAP would arise from the high electronegativity of oxygen; specific frontier orbitals of the TriAAOP π-systems were energetically stabilized relative to those of the TADAP π-system. The present findings corroborate that the meso-modification of a porphyrin rings with different kinds of heteroatoms is a promising strategy to fine tune their light-response properties that are switchable by reversible single electron transfer processes.

元の言語英語
記事番号e21456
ジャーナルHeteroatom Chemistry
29
発行部数5-6
DOI
出版物ステータス出版済み - 12 1 2018

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Zinc
Porphyrins
Optical properties
21-oxaporphyrin
Oxidation-Reduction
Oxygen
Derivatives
Oxidation
Electronegativity
Cyclization
Electrochemical properties
Silver
Oxidants
Nuclear magnetic resonance spectroscopy
Density functional theory
Cations
Metals
Electrons

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

これを引用

Synthesis and properties of redox-switchable zinc complexes of 10,15,20-triaryl-15-aza-5-oxaporphyrin. / Sudoh, Keisuke; Furukawa, Ko; Nakano, Haruyuki; Shimizu, Soji; Matano, Yoshihiro.

:: Heteroatom Chemistry, 巻 29, 番号 5-6, e21456, 01.12.2018.

研究成果: ジャーナルへの寄稿記事

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abstract = "The synthesis, aromaticity, and optical and electrochemical properties of zinc(II) complexes of 10,15,20-triaryl-15-aza-5-oxaporphyrin (TriAAOP) were investigated. Metal-templated cyclization of a zinc(II) 1,19-dichloro-5,10,15-triaryl-10-azatetrapyrrin complex with an oxygen source afforded 20π TriAAOP in the neutral form. Oxidation of 20π TriAAOP with silver (I) hexafluorophosphate generated the 19π radical cation or 18π dication depending on the content of oxidant used. The interconversion between the three oxidation states (18π, 19π, and 20π) resulted in distinct changes in the aromaticity and optical properties of the 15-aza-5-oxaporphyrin π-system. Nuclear magnetic resonance spectroscopy of 20π TriAAOP revealed its antiaromatic character, whereas that of the 18π TriAAOP dication showed its aromatic character. The combined effect of the two meso-heteroatoms was directly reflected in the redox properties of the porphyrin ring; TriAAOP was reduced more easily and more difficult to oxidize than the zinc(II) complex of 5,10,15,20-tetraaryl-5,15-diaz-aporphyrin (TADAP). In the ultraviolet-visible-near–infrared spectra of the materials, the lowest-energy electronic excitations of the 19π and 18π TriAAOP derivatives were considerably red-shifted compared with those of the isoelectronic TADAP derivatives. Based on the results of density functional theory calculations, it was concluded that the observed differences between TriAAOP and TADAP would arise from the high electronegativity of oxygen; specific frontier orbitals of the TriAAOP π-systems were energetically stabilized relative to those of the TADAP π-system. The present findings corroborate that the meso-modification of a porphyrin rings with different kinds of heteroatoms is a promising strategy to fine tune their light-response properties that are switchable by reversible single electron transfer processes.",
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T1 - Synthesis and properties of redox-switchable zinc complexes of 10,15,20-triaryl-15-aza-5-oxaporphyrin

AU - Sudoh, Keisuke

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AU - Matano, Yoshihiro

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