Alternating Covalent Bonding Interactions in a One-Dimensional Chain of a Phenalenyl-Based Singlet Biradical Molecule Having Kekulé Structures
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- Akihiro Shimizu
- Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan, and Department of Chemistry and Material Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
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- Takashi Kubo
- Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan, and Department of Chemistry and Material Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
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- Mikio Uruichi
- Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan, and Department of Chemistry and Material Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
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- Kyuya Yakushi
- Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan, and Department of Chemistry and Material Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
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- Masayoshi Nakano
- Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan, and Department of Chemistry and Material Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
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- Daisuke Shiomi
- Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan, and Department of Chemistry and Material Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
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- Kazunobu Sato
- Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan, and Department of Chemistry and Material Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
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- Takeji Takui
- Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan, and Department of Chemistry and Material Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
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- Yasukazu Hirao
- Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan, and Department of Chemistry and Material Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
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- Kouzou Matsumoto
- Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan, and Department of Chemistry and Material Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
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- Hiroyuki Kurata
- Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan, and Department of Chemistry and Material Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
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- Yasushi Morita
- Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan, and Department of Chemistry and Material Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
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- Kazuhiro Nakasuji
- Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan, and Department of Chemistry and Material Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
説明
A novel naphthoquinoid singlet biradical (2a) stabilized by phenalenyl rings is prepared by a multistep procedure and is investigated in terms of covalent bonding interactions. The molecule 2a gives single crystals, in which a 1D chain is formed with a very short π-π contact at the overlapping phenalenyl rings. The unpaired electrons in 2a are involved in covalent bonding interactions not only within the molecule but also between the molecules in the 1D chain, and a linear conjugation is made of the alternating intra- and intermolecular covalent bonding interactions through conventional π-conjugation and multicenter bonding, respectively. The linear conjugation causes a lower-energy shift of the optical transition band in the crystal, but the transition energy is higher than that of the benzoquinoid singlet biradical (1a). This optical behavior and the magnetic susceptibility measurements reveal that the intermolecular covalent bonding interaction in the 1D chain of 2a is greater in strength than the intramolecular one, despite the fact that a fully conjugated Kekulé structure can be drawn for 2a.
収録刊行物
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- Journal of the American Chemical Society
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Journal of the American Chemical Society 132 (41), 14421-14428, 2010-09-27
American Chemical Society (ACS)
