A Stable Organic π‐Radical of a Zinc(II)–Copper(I)–Zinc(II) Complex of Decaphyrin |
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| Authors: | Dr Yasuo Tanaka Dr Tomoki Yoneda Prof?Dr Ko Furukawa Dr Taro Koide Hirotaka Mori Dr Takayuki Tanaka Prof?Dr Hiroshi Shinokubo Prof?Dr Atsuhiro Osuka |
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| Institution: | 1. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo‐ku, Kyoto 606‐8502 (Japan);2. Center for Instrumental Analysis, Niigata University, Nishi‐ku, Niigata 950‐2181 (Japan);3. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa‐ku, Nagoya, 464‐8603 (Japan) |
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| Abstract: | A ZnII‐CuI‐ZnII heterotrimetal complex of decaphyrin was synthesized by stepwise metalations: metalation of a 46]decaphyrin with ZnII ions to produce a 46π decaphyrin bis(ZnII) complex and its subsequent metalation with CuII ion. In the second metalation step, it has been shown that CuII ion is reduced to a CuI ion in the complex and a dianionic bis(ZnII) 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. |
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| Keywords: | copper decaphyrin expanded porphyrins heterometal complexes stable radicals |
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