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

43 Citations (Scopus)

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
Publication status	Published - 2016 Jul 18

Bibliographical note

Funding Information:
The research at Kyoto was supported by Grants-in-Aid from MEXT (No.: 25107002 “Science of Atomic Layers”) and from JSPS (No.: 25220802 (Scientific Research (S)), 24685007 (Young Scientists (A)), and 26620081 (Exploratory Research)), and by ACT-C, JST. We thank Prof. Dr. Hiroshi Kitagawa and Dr. Kazuya Otsubo (Kyoto University) for XRPD measurements. H.Y. thanks Kansai Research Foundation for Technology Promotion and The Asahi Glass Foundation for financial support. The research at Yonsei University was supported by the Ministry of Science, ICT & Future, Korea through the Global Research Laboratory Program (2013K1A1A2A02050183).

Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)

Access to Document

10.1002/anie.201602683

Cite this

@article{be03afb2e5de471cb90f716a90e24a96,

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.",

author = "Kenichi Kato and Wonhee Cha and Juwon Oh and Ko Furukawa and Hideki Yorimitsu and Dongho Kim and Atsuhiro Osuka",

note = "Funding Information: The research at Kyoto was supported by Grants-in-Aid from MEXT (No.: 25107002 “Science of Atomic Layers”) and from JSPS (No.: 25220802 (Scientific Research (S)), 24685007 (Young Scientists (A)), and 26620081 (Exploratory Research)), and by ACT-C, JST. We thank Prof. Dr. Hiroshi Kitagawa and Dr. Kazuya Otsubo (Kyoto University) for XRPD measurements. H.Y. thanks Kansai Research Foundation for Technology Promotion and The Asahi Glass Foundation for financial support. The research at Yonsei University was supported by the Ministry of Science, ICT & Future, Korea through the Global Research Laboratory Program (2013K1A1A2A02050183). Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2016",

month = jul,

day = "18",

doi = "10.1002/anie.201602683",

language = "English",

volume = "55",

pages = "8711--8714",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "30",

}

TY - JOUR

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

N1 - Funding Information: The research at Kyoto was supported by Grants-in-Aid from MEXT (No.: 25107002 “Science of Atomic Layers”) and from JSPS (No.: 25220802 (Scientific Research (S)), 24685007 (Young Scientists (A)), and 26620081 (Exploratory Research)), and by ACT-C, JST. We thank Prof. Dr. Hiroshi Kitagawa and Dr. Kazuya Otsubo (Kyoto University) for XRPD measurements. H.Y. thanks Kansai Research Foundation for Technology Promotion and The Asahi Glass Foundation for financial support. The research at Yonsei University was supported by the Ministry of Science, ICT & Future, Korea through the Global Research Laboratory Program (2013K1A1A2A02050183). Publisher Copyright: © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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.

UR - http://www.scopus.com/inward/record.url?scp=84973307898&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84973307898&partnerID=8YFLogxK

U2 - 10.1002/anie.201602683

DO - 10.1002/anie.201602683

M3 - Article

AN - SCOPUS:84973307898

SN - 1433-7851

VL - 55

SP - 8711

EP - 8714

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 30

ER -

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

Abstract

Bibliographical note

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this