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A Stable Organic π‐Radical of a Zinc(II)–Copper(I)–Zinc(II) Complex of Decaphyrin
Author(s) -
Tanaka Yasuo,
Yoneda Tomoki,
Furukawa Ko,
Koide Taro,
Mori Hirotaka,
Tanaka Takayuki,
Shinokubo Hiroshi,
Osuka Atsuhiro
Publication year - 2015
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.201505130
Subject(s) - metalation , chemistry , zinc , ligand (biochemistry) , delocalized electron , unpaired electron , copper , moiety , inorganic chemistry , ion , photochemistry , stereochemistry , molecule , organic chemistry , biochemistry , receptor
A Zn II ‐Cu I ‐Zn II heterotrimetal complex of decaphyrin was synthesized by stepwise metalations: metalation of a [46]decaphyrin with Zn II ions to produce a 46π decaphyrin bis(Zn II ) complex and its subsequent metalation with Cu II ion. In the second metalation step, it has been shown that Cu II ion is reduced to a Cu I ion in the complex and a dianionic bis(Zn II ) containing [46]decaphyrin ligand is oxidized to the corresponding monoanionic [45]decaphyrin ligand, indicating a non‐innocent nature of the decaphyrin ligand. Despite the radical nature, the heterotrimetal complex is fairly stable under ambient conditions and exhibits almost no intermolecular magnetic interaction, owing to extensive delocalization of an unpaired electron in the large π‐conjugated circuit of decaphyrin moiety.