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. 2024 Feb 7;30(8):e202303456.
doi: 10.1002/chem.202303456. Epub 2023 Dec 19.

A Nitronyl Nitroxide-Substituted Benzotriazinyl Tetraradical

Evgeny V Tretyakov  1 , Igor A Zayakin  1 , Alexey A Dmitriev  2 , Matvey V Fedin  3 , Galina V Romanenko  3 , Artem S Bogomyakov  3 , Anna Ya Akyeva  1 , Mikhail A Syroeshkin  1 , Naoki Yoshioka  4 , Nina P Gritsan  2
Affiliations

A Nitronyl Nitroxide-Substituted Benzotriazinyl Tetraradical

Evgeny V Tretyakov et al. Chemistry. .

Abstract

High-spin organic tetraradicals with significant intramolecular exchange interactions have high potential for advanced technological applications and fundamental research, but those synthesized to date possess limited stability and processability. In this work, we have designed a tetraradical based on the Blatter's radical and nitronyl nitroxide radical moieties and successfully synthesized it by using the palladium-catalyzed cross-coupling reaction of a triiodo-derivative of the 1,2,4-benzotriazinyl radical with gold(I) nitronyl nitroxide-2-ide complex in the presence of a newly developed efficient catalytic system. The molecular and crystal structure of the tetraradical was confirmed by X-ray diffraction analysis. The tetraradical possesses good thermal stability with decomposition onset at ∼150 °C under an inert atmosphere and exhibits reversible redox waves at -0.54 and 0.45 V versus Ag/AgCl. The magnetic properties of the tetraradical were characterized by SQUID magnetometry of polycrystalline powders and EPR spectroscopy in various matrices. The collected data, analyzed by using high-level quantum chemical calculations, confirmed that the tetraradical has a triplet ground state and a nearby excited quintet state. The unique high stability of the prepared triazinyl-nitronylnitroxide tetraradical is a new milestone in the field of creating high-spin systems.

Keywords: benzotriazinyl radicals; high-spin molecules; multispin organic systems; nitronyl nitroxides; tetraradicals.

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