2-(8-Iodonaphthalen-1-yl)-Substituted Nitronyl Nitroxide: Suppressed Reactivity of Iodine Atom and Unusual Temperature Dynamics of the EPR Spectrum

2-(8-Iodonaphthalen-1-yl)-Substituted Nitronyl Nitroxide: Suppressed Reactivity of Iodine Atom and Unusual Temperature Dynamics of the EPR Spectrum Научная публикация

Журнал

European Journal of Organic Chemistry
ISSN: 1434-193X , E-ISSN: 1099-0690

Вых. Данные

Год: 2021, Том: 2021, Номер: 17, Страницы: 2355-2361 Страниц : 7 DOI: 10.1002/ejoc.202100138

Ключевые слова

Computational chemistry; Diradicals; Exchange interactions; Nitronyl nitroxides; Radicals

Авторы

Tretyakov E.V. ¹ , Lomanovich K.A. ² , Bagryanskaya E.G. ² , Romanenko G.V. ³ , Bogomyakov A.S. ³ , Zueva E.M. ⁴ , Petrova M.M. ⁴ , Dmitriev A.A. ⁵ , Gritsan N.P. ⁵

Организации

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect, 47, Moscow, 119991, Russian Federation
2	N. N. Vorozhtsov Institute of Organic Chemistry, Siberian Branch of Russian Academy of Sciences, 9 Ac. Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation
3	International Tomography Center, Siberian Branch of Russian Academy of Sciences, 3a Institutskaya Str., Novosibirsk, 630090, Russian Federation
4	Kazan National Research Technological University, 68 K. Marx Str., Kazan, 420015, Russian Federation
5	V.V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of Russian Academy of Sciences, 3 Institutskaya Str., Novosibirsk, 630090, Russian Federation

While developing methods for obtaining high-spin graphene nanostructures, we carried out a model cross-coupling reaction between 1,8-diiodonaphthalene and an organogold derivative of a nitronyl nitroxide. It was found that only one iodine atom reacted, leading to the corresponding 8-iodonaphthalen-1-yl-substituted nitronyl nitroxide. The latter was successfully isolated as two polymorphic modifications, whose X-ray structural analysis revealed a strong distortion of the paramagnet's geometry in comparison with a noniodinated analog. Moreover, the spatial proximity of the heavy iodine atom and the paramagnetic moiety resulted in unprecedented temperature dynamics of the EPR spectrum. To clarify these dynamics, quantum chemical calculations were performed using the exact two-component relativistic X2C method with the self-consistent account of spin-orbit coupling in conjunction with the B3LYP functional and relativistic STO-type basis set. These computations predicted a reasonable aiso(127I) value that can affect the EPR spectrum. Substitution of the second iodine atom would lead to the formation of a diradical with a 1,8-naphthalenediyl bridge, whose structure and magnetic properties were analyzed at the DFT level. Two stable conformations of the diradical with strongly distorted geometry were identified. In both conformations, calculations predict a ferromagnetic exchange between the paramagnetic centers with J=8 and 14 cm−1 (H=−2 J⋅S1S2). © 2021 Wiley-VCH GmbH

Tretyakov E.V. , Lomanovich K.A. , Bagryanskaya E.G. , Romanenko G.V. , Bogomyakov A.S. , Zueva E.M. , Petrova M.M. , Dmitriev A.A. , Gritsan N.P.
2-(8-Iodonaphthalen-1-yl)-Substituted Nitronyl Nitroxide: Suppressed Reactivity of Iodine Atom and Unusual Temperature Dynamics of the EPR Spectrum
European Journal of Organic Chemistry. 2021. V.2021. N17. P.2355-2361. DOI: 10.1002/ejoc.202100138 WOS Scopus РИНЦ

Опубликована online:	24 мар. 2021 г.
Опубликована в печати:	7 мая 2021 г.

Web of science	WOS:000631916200001
Scopus	2-s2.0-85103225402
РИНЦ	46759824
OpenAlex	W3133800607