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Redox‐Induced Modulation of Exchange Interaction in a High‐Spin Ground‐State Diradical/Triradical System
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 conditio...
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Published in: | Chemistry : a European journal 2020-03, Vol.26 (14), p.3166-3172 |
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Main Authors: | , , , , , , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | 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.
Higher order exchange coupling: Oxidation of a diradical bis(nitronyl nitroxide)‐substituted diphenyldihydrophenazine introduces an additional electronic spin at the dihydrophenazine core, which results in a cationic quartet ground‐state species with stronger ferromagnetic coupling in comparison with that of the neutral triplet‐state species. Reversible conversion between the two species is confirmed from the electronic spectra acquired during electrochemical reactions. |
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ISSN: | 0947-6539 1521-3765 |
DOI: | 10.1002/chem.201905465 |