Cooperative Supramolecular Engineering: Dual-Mode Halogen and Hydrogen Bonding for Enhancement of Exchange Interactions in Nitronyl Nitroxide Systems

Cooperative Supramolecular Engineering: Dual-Mode Halogen and Hydrogen Bonding for Enhancement of Exchange Interactions in Nitronyl Nitroxide Systems Full article

Journal

Crystal Growth & Design
ISSN: 1528-7483 , E-ISSN: 1528-7505

Output data

Year: 2026, Volume: 26, Number: 3, Pages: 1403-1413 Pages count : 11 DOI: 10.1021/acs.cgd.5c01594

Authors

Shurikov Matvey K. ¹ , Kolesnikova Yuliana A. ¹ , Chernavin Platon A. ² , Ivanov Daniil M. ³ , Smirnova Kristina A. ² , Kovalskaya Ekaterina S. ¹ , Gorbunov Dmitry E. ⁴ , Gritsan Nina P. ⁴ , Bogomyakov Artem S. ² , Tretyakov Evgeny V. ⁵ , Burguera Sergi ^6,7 , Frontera Antonio ⁶ , Resnati Giuseppe ⁷ , Kukushkin Vadim Yu. ³ , Petunin Pavel V. ¹ , Postnikov Pavel S. ^1,8

Affiliations

1	Research School of Chemistry & Applied Biomedical Sciences, Tomsk Polytechnic University, Lenin Av. 30, Tomsk 634050, Russian Federation
2	International Tomography Center, Siberian Branch of the Russian Academy of Sciences, Institutskaya Str. 3a, Novosibirsk 630090, Russian Federation
3	Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg 199034, Russian Federation
4	V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Institutskaya Str. 3, Novosibirsk 630090, Russian Federation
5	N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Av. 47, Moscow 119991, Russian Federation
6	Departament de Química, Universitat de les Illes Balears, 07122 Palma de Mallorca(Baleares), Spain
7	NFMLab, Department of Chemistry, Materials and Chemical Engineering “Giulio Natta”, Politecnico di Milano, via Mancinelli 7, I-20131 Milano, Italy
8	N. N. Vorozhtsov Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Lavrentiev Av. 9, Novosibirsk 630090, Russian Federation

This work presents a novel cooperative supramolecular engineering strategy based on the simultaneous utilization of halogen bonding (I···N) and hydrogen bonding (H···N) interactions for the directed self-assembly of three structurally distinct nitronyl nitroxide radicals: 2-(4-iodophenyl)-4,4,5,5-tetramethylimidazolin-1-oxyl-3-oxide (1), 2-(4-iodoethynylphenyl)-4,4,5,5-tetramethylimidazolin-1-oxyl-3-oxide (2), and 2-(2,3,5,6-tetrafluoro-4-iodophenyl)-4,4,5,5-tetramethylimidazolin-1-oxyl-3-oxide (3) with 1,4-diazabicyclo[2.2.2]octane (DABCO). We synthesized and characterized cocrystals (1–3)·DABCO containing these iodine-substituted nitronyl nitroxide radicals with varied electronic properties. The primary novelty lies in demonstrating that cooperative dual-mode noncovalent assembly significantly outperforms single-interaction approaches, achieving quantitative enhancement of magnetic exchange interactions by nearly two orders of magnitude from approximately 0 K for unassociated radicals to −78 K for supramolecular assemblies. The 3·DABCO system approaches the literature benchmark for purely organic nitronyl nitroxide materials, representing a substantial advancement in metal-free magnetic coupling strength. Comprehensive theoretical analysis using DFT, energy decomposition analysis, natural bond orbital analysis, and quantum theory of atoms in molecules elucidated the mechanistic basis for cooperative enhancement, revealing orthogonal energetic profiles where halogen bonds exhibit predominantly electrostatic character with significant orbital contributions, while hydrogen bonds show dispersive dominance with minimal orbital involvement. This complementary nature enables additive stabilization without competitive interference between interaction modes. The methodology addresses inherent limitations of single-interaction approaches, providing enhanced predictability and tunability compared with serendipitous discoveries.

Shurikov M.K. , Kolesnikova Y.A. , Chernavin P.A. , Ivanov D.M. , Smirnova K.A. , Kovalskaya E.S. , Gorbunov D.E. , Gritsan N.P. , Bogomyakov A.S. , Tretyakov E.V. , Burguera S. , Frontera A. , Resnati G. , Kukushkin V.Y. , Petunin P.V. , Postnikov P.S.
Cooperative Supramolecular Engineering: Dual-Mode Halogen and Hydrogen Bonding for Enhancement of Exchange Interactions in Nitronyl Nitroxide Systems
Crystal Growth & Design. 2026. V.26. N3. P.1403-1413. DOI: 10.1021/acs.cgd.5c01594 WOS Scopus OpenAlex

Submitted:	Nov 10, 2025
Published online:	Feb 4, 2026

Web of science:	WOS:001668753600001
Scopus:	2-s2.0-105030188519
OpenAlex:	W7125602260

DB	Citing
OpenAlex	Нет цитирований
Scopus	Нет цитирований