Halogen bonding promotes ferromagnetic exchange in nitronyl nitroxide radicals: A quantitative analysis

Halogen bonding promotes ferromagnetic exchange in nitronyl nitroxide radicals: A quantitative analysis Научная публикация

Журнал

Materials Chemistry and Physics
ISSN: 1879-3312

Вых. Данные

Год: 2025, Том: 332, Номер статьи : 130252, Страниц : DOI: 10.1016/j.matchemphys.2024.130252

Авторы

Kudryavtseva Ekaterina N. ¹ , Tretyakov Evgeny V. ¹ , Gomila Rosa M. ² , Frontera Antonio ² , Dmitriev Alexey A. ³ , Gritsan Nina P. ³ , Xia Debin ⁴ , Efimov Nikolay N. ⁵ , Petunin Pavel V. ⁶ , Postnikov Pavel S. ⁶ , Romanenko Galina V. ⁷ , Kukushkin Vadim Yu. ⁸

Организации

1	N. D. Zelinsky Institute of Organic Chemistry, Leninsky Av. 47, Moscow, 119991, Russian Federation
2	Department of Chemistry, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122, Palma de Mallorca, Spain
3	V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Institutskaya Str. 3, Novosibirsk, 630090, Russian Federation
4	MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, 150001, PR China
5	N. S. Kurnakov Institute of General and Inorganic Chemistry, Leninsky Av. 31, Moscow, 119991, Russian Federation
6	Research School of Chemistry & Applied Biomedical Sciences, Tomsk Polytechnic University, Lenin Av. 30, Tomsk, 634050, Russian Federation
7	International Tomography Center, Institutskaya Str. 3a, 630090, Novosibirsk, Russian Federation
8	Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg, 199034, Russian Federation

Organic nitroxide radicals – specifically chloro-, bromo, and iodo-substituted nitronyl nitroxides – exhibit self-assembly in crystalline states through the combined action of halogen (Hal···ONO) and hydrogen (ONO⋯HMe) bonds. Theoretical calculations reveal that halogen bonds primarily govern the association of these nitroxides. This halogen bonding facilitates the proximity of atoms carrying spin densities of opposite signs, thereby promoting ferromagnetic intermolecular exchange interactions. This research demonstrates, for the first time, that halogen bonding can establish channels facilitating ferromagnetic intermolecular exchange between paramagnetic centers in organic nitronyl nitroxide radicals. This breakthrough discovery expands the potential applications of halogen bonding in the supramolecular modulation of magnetic properties within high-spin clusters—a function that was previously attributed exclusively to hydrogen bonding.

Kudryavtseva E.N. , Tretyakov E.V. , Gomila R.M. , Frontera A. , Dmitriev A.A. , Gritsan N.P. , Xia D. , Efimov N.N. , Petunin P.V. , Postnikov P.S. , Romanenko G.V. , Kukushkin V.Y.
Halogen bonding promotes ferromagnetic exchange in nitronyl nitroxide radicals: A quantitative analysis
Materials Chemistry and Physics. 2025. V.332. 130252 . DOI: 10.1016/j.matchemphys.2024.130252 WOS Scopus

Опубликована в печати:

15 февр. 2025 г.

Web of science:	WOS:001388696400001
Scopus:	2-s2.0-85211434824

БД	Цитирований
Scopus	3
Web of science	4