Premium
Spontaneous Formation of an Air‐Stable Radical upon the Direct Fusion of Diphenylmethane to a Triarylporphyrin
Author(s) -
Kato Kenichi,
Cha Wonhee,
Oh Juwon,
Furukawa Ko,
Yorimitsu Hideki,
Kim Dongho,
Osuka Atsuhiro
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201602683
Subject(s) - diphenylmethane , radical , photochemistry , radical ion , chemistry , hydrogen atom , porphyrin , delocalized electron , spectroscopy , electrochemistry , absorption (acoustics) , ion , materials science , organic chemistry , alkyl , physics , quantum mechanics , composite material , catalysis , electrode
The direct fusion of a diphenylmethane segment to a Ni II 5,10,15‐triarylporphyrin with three linkages furnished an air‐ and moisture‐stable neutral radical through unexpected and spontaneous oxidation. This radical was demetalated by treatment with H 2 SO 4 and CF 3 CO 2 H 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.