Redox-Induced Modulation of Exchange Interaction in a High-Spin Ground-State Diradical/Triradical System.

Autor: Nagata A; Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, Osaka, 558-8585, Japan., Hiraoka S; Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, Osaka, 558-8585, Japan., Suzuki S; Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, Osaka, 558-8585, Japan.; Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan., Kozaki M; Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, Osaka, 558-8585, Japan.; Osaka City University, Advanced Research Institute for, Natural Science and Technology (OCARINA), Sumiyoshi-ku, Osaka, Osaka, 558-8585, Japan., Shiomi D; Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, Osaka, 558-8585, Japan., Sato K; Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, Osaka, 558-8585, Japan., Takui T; Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, Osaka, 558-8585, Japan., Tanaka R; X-ray Crystal Analysis Laboratory, Graduate School of Engineering, Osaka City University, Sumiyoshi-ku, Osaka, Osaka, 558-8585, Japan., Okada K; Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, Osaka, 558-8585, Japan.; Osaka City University, Advanced Research Institute for, Natural Science and Technology (OCARINA), Sumiyoshi-ku, Osaka, Osaka, 558-8585, Japan.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2020 Mar 09; Vol. 26 (14), pp. 3166-3172. Date of Electronic Publication: 2020 Feb 21.
DOI: 10.1002/chem.201905465
Abstrakt: A triplet ground-state diradical molecule, bis(nitronyl nitroxide)-substituted diphenyldihydrophenazine (1 .. ), that can be converted into a one-electron oxidized species, 1 …+ , in the quartet ground state has been developed. Surprisingly, these species, 1 .. and 1 …+ , can be used under ambient conditions because they are reasonably stable under aerobic conditions, even in solution. The temperature-dependent magnetic susceptibilities reveal that 1 .. and 1 …+ are in the triplet state, with a weak exchange interaction (J 1 /k B = +3.1 K) and quartet ground state with a strong exchange interaction (J 2 /k B = +160 K), respectively. The interconversion between the neutral and one-electron oxidized species can be realized through electrochemical reactions. Significantly different absorption bands in the near-IR region newly appeared in the electronic spectra acquired during electrochemical oxidation/reduction.
(© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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