Nitronyl Nitroxide‐Substituted Benzotriazinyl Tetraradical

Nitronyl Nitroxide‐Substituted Benzotriazinyl Tetraradical Full article

Journal

Chemistry: A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765

Output data

Year: 2024, Volume: 30, Number: 8, Article number : e202303456, Pages count : DOI: 10.1002/chem.202303456

Authors

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

Affiliations

1	Zelinsky Institute of Organic Chemistry RAS: FGBUN Institut organiceskoj himii imeni N D Zelinskogo Rossijskoj akademii nauk, Leninsky Av. 47, 119991 Moscow, RUSSIAN FEDERATION
2	Voevodsky Institute of Chemical Kinetics and Combustion SB RAS: Institut himiceskoj kinetiki i gorenia imeni V V Voevodskogo SO RAN, Laboratory of Quantum Chemistry and Computer Simulation, RUSSIAN FEDERATION
3	International Tomography Center SB RAS: Mezdunarodnyj tomograficeskij centr SO RAN, RUSSIAN FEDERATION
4	Keio University Faculty of Science and Technology Graduate School of Science and Technology: Keio Gijuku Daigaku Rikogakubu Daigakuin Rikogaku Kenkyuka, Department of Applied Chemistry, JAPAN

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.

Tretyakov E. , Zayakin I. , Dmitriev A. , Fedin M. , Romanenko G. , Bogomyakov A. , Akyeva A. , Syroeshkin M. , Yoshioka N. , Gritsan N.
Nitronyl Nitroxide‐Substituted Benzotriazinyl Tetraradical
Chemistry: A European Journal. 2024. V.30. N8. e202303456 . DOI: 10.1002/chem.202303456 WOS OpenAlex

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