title: A Stable Organic π-Radical of a Zinc(II)-Copper(I)-Zinc(II) Complex of Decaphyrin.
abstract: 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.
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan).
authors.forename: Yasuo
authors.initials: Y
authors.lastname: Tanaka
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan).
authors.forename: Tomoki
authors.initials: T
authors.lastname: Yoneda
authors.affiliation: Center for Instrumental Analysis, Niigata University, Nishi-ku, Niigata 950-2181 (Japan). kou-f@chem.sc.niigata-u.ac.jp.
authors.forename: Ko
authors.initials: K
authors.lastname: Furukawa
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan).
authors.forename: Taro
authors.initials: T
authors.lastname: Koide
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan).
authors.forename: Hirotaka
authors.initials: H
authors.lastname: Mori
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan).
authors.forename: Takayuki
authors.initials: T
authors.lastname: Tanaka
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya, 464-8603 (Japan).
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Shinokubo
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan). osuka@kuchem.kyoto-u.ac.jp.
authors.forename: Atsuhiro
authors.initials: A
authors.lastname: Osuka
keywords: copper; decaphyrin; expanded porphyrins; heterometal complexes; stable radicals