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 Full article

Journal

European Journal of Organic Chemistry
ISSN: 1434-193X

Output data

Year: 2021, Volume: 2021, Number: 17, Pages: 2355-2361 Pages count : 7 DOI: 10.1002/ejoc.202100138

Tags

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

Authors

Tretyakov Evgeny V. ¹ , Lomanovich Konstantin A. ² , Bagryanskaya Elena G. ² , Romanenko Galina V. ³ , Bogomyakov Artem S. ³ , Zueva Ekaterina M. ⁴ , Petrova Maria M. ⁴ , Dmitriev Alexey A. ⁵ , Gritsan Nina P. ⁵

Affiliations

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

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 computa- tions predicted a reasonable aiso( 127 I) 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 conforma- tions, calculations predict a ferromagnetic exchange between the paramagnetic centers with J=8 and 14 cm 1 (H= 2 J·S1S2).

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

Published print:

May 7, 2021

Web of science:	WOS:000631916200001
Scopus:	2-s2.0-85103225402

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