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. 2015 Sep 7;54(37):10908-11.
doi: 10.1002/anie.201505130. Epub 2015 Jul 17.

A Stable Organic π-Radical of a Zinc(II)-Copper(I)-Zinc(II) Complex of Decaphyrin

Yasuo Tanaka  1 , Tomoki Yoneda  1 , Ko Furukawa  2 , Taro Koide  1 , Hirotaka Mori  1 , Takayuki Tanaka  1 , Hiroshi Shinokubo  3 , Atsuhiro Osuka  4
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A Stable Organic π-Radical of a Zinc(II)-Copper(I)-Zinc(II) Complex of Decaphyrin

Yasuo Tanaka et al. Angew Chem Int Ed Engl. .

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.

Keywords: copper; decaphyrin; expanded porphyrins; heterometal complexes; stable radicals.

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