Spontaneous Formation of an Air-Stable Radical upon the Direct Fusion of Diphenylmethane to a Triarylporphyrin

Kenichi Kato; Wonhee Cha; Juwon Oh; Ko Furukawa; Hideki Yorimitsu; Dongho Kim; Atsuhiro Osuka

doi:10.1002/anie.201602683

Spontaneous Formation of an Air-Stable Radical upon the Direct Fusion of Diphenylmethane to a Triarylporphyrin

Kenichi Kato, Wonhee Cha, Juwon Oh, Ko Furukawa, Hideki Yorimitsu, Dongho Kim, Atsuhiro Osuka

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

50 Scopus citations

Abstract

The direct fusion of a diphenylmethane segment to a Ni^II5,10,15-triarylporphyrin with three linkages furnished an air- and moisture-stable neutral radical through unexpected and spontaneous oxidation. This radical was demetalated by treatment with H₂SO₄and CF₃CO₂H to provide the corresponding free-base radical. These porphyrin radicals are very stable owing to spin delocalization and have been fully characterized through UV/Vis/NIR absorption spectroscopy, X-ray crystallographic analysis, magnetic susceptibility measurements, electrochemical studies, laser-based ultrafast spectroscopic studies, and theoretical calculations. They were chemically oxidized and reduced to the corresponding cation and anion but did not react with hydrogen-atom donors.

Original language	English
Pages (from-to)	8711-8714
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	30
DOIs	https://doi.org/10.1002/anie.201602683
State	Published - 18 Jul 2016

Keywords

aromaticity
fused-ring systems
porphyrinoids
radical
redox chemistry

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title = "Spontaneous Formation of an Air-Stable Radical upon the Direct Fusion of Diphenylmethane to a Triarylporphyrin",

abstract = "The direct fusion of a diphenylmethane segment to a NiII5,10,15-triarylporphyrin with three linkages furnished an air- and moisture-stable neutral radical through unexpected and spontaneous oxidation. This radical was demetalated by treatment with H2SO4and CF3CO2H to provide the corresponding free-base radical. These porphyrin radicals are very stable owing to spin delocalization and have been fully characterized through UV/Vis/NIR absorption spectroscopy, X-ray crystallographic analysis, magnetic susceptibility measurements, electrochemical studies, laser-based ultrafast spectroscopic studies, and theoretical calculations. They were chemically oxidized and reduced to the corresponding cation and anion but did not react with hydrogen-atom donors.",

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T1 - Spontaneous Formation of an Air-Stable Radical upon the Direct Fusion of Diphenylmethane to a Triarylporphyrin

AU - Kato, Kenichi

AU - Cha, Wonhee

AU - Oh, Juwon

AU - Furukawa, Ko

AU - Yorimitsu, Hideki

AU - Kim, Dongho

AU - Osuka, Atsuhiro

PY - 2016/7/18

Y1 - 2016/7/18

N2 - The direct fusion of a diphenylmethane segment to a NiII5,10,15-triarylporphyrin with three linkages furnished an air- and moisture-stable neutral radical through unexpected and spontaneous oxidation. This radical was demetalated by treatment with H2SO4and CF3CO2H to provide the corresponding free-base radical. These porphyrin radicals are very stable owing to spin delocalization and have been fully characterized through UV/Vis/NIR absorption spectroscopy, X-ray crystallographic analysis, magnetic susceptibility measurements, electrochemical studies, laser-based ultrafast spectroscopic studies, and theoretical calculations. They were chemically oxidized and reduced to the corresponding cation and anion but did not react with hydrogen-atom donors.

AB - The direct fusion of a diphenylmethane segment to a NiII5,10,15-triarylporphyrin with three linkages furnished an air- and moisture-stable neutral radical through unexpected and spontaneous oxidation. This radical was demetalated by treatment with H2SO4and CF3CO2H to provide the corresponding free-base radical. These porphyrin radicals are very stable owing to spin delocalization and have been fully characterized through UV/Vis/NIR absorption spectroscopy, X-ray crystallographic analysis, magnetic susceptibility measurements, electrochemical studies, laser-based ultrafast spectroscopic studies, and theoretical calculations. They were chemically oxidized and reduced to the corresponding cation and anion but did not react with hydrogen-atom donors.

KW - aromaticity

KW - fused-ring systems

KW - porphyrinoids

KW - radical

KW - redox chemistry

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JF - Angewandte Chemie - International Edition

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Spontaneous Formation of an Air-Stable Radical upon the Direct Fusion of Diphenylmethane to a Triarylporphyrin

Abstract

Keywords

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