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A Highly Oxidized Cobalt Porphyrin Dimer: Spin Coupling and Stabilization of the Four‐Electron Oxidation Product
Author(s) -
Dey Soumyajit,
Sil Debangsu,
Rath Sankar Prasad
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.201509430
Subject(s) - porphyrin , cobalt , photochemistry , dimer , chemistry , radical , singlet state , crystallography , inorganic chemistry , organic chemistry , excited state , physics , nuclear physics
A highly oxidized cobalt porphyrin dimer is reported. Each cobalt(II) ion and porphyrin ring underwent 1e oxidation with iodine as the oxidant to give a 4e‐oxidized cobalt(III) porphyrin π‐cation radical dimer. The bridging ethylene group allows for substantial conjugation of the porphyrin macrocycles, thus leading to a strong antiferromagnetic coupling between the π‐cation radicals and to stabilization of the singlet state. X‐ray crystallography clearly showed that the complex may be considered as a real supramolecule rather than two cobalt(III) porphyrin π‐cation radicals that interact through space.