Redox-Induced Modulation of Exchange Interaction in a High-Spin Ground-State Diradical/Triradical System |
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Authors: | Atsuki Nagata Shinsuke Hiraoka Dr Shuichi Suzuki Prof Dr Masatoshi Kozaki Prof Dr Daisuke Shiomi Prof Dr Kazunobu Sato Prof Dr Takeji Takui Dr Rika Tanaka Prof Dr Keiji Okada |
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Institution: | 1. Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, Osaka, 558-8585 Japan;2. X-ray Crystal Analysis Laboratory, Graduate School of Engineering, Osaka City University, Sumiyoshi-ku, Osaka, Osaka, 558-8585 Japan |
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Abstract: | 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 (J1/kB = +3.1 K) and quartet ground state with a strong exchange interaction (J2/kB = +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. |
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Keywords: | electronic structure magnetic properties radical ions redox chemistry structure elucidation |
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