TY - JOUR

T1 - Halogen Bonding as a Supramolecular Modulator of Crystal Packing and Exchange Interactions in Nitronyl Nitroxides

AU - Petunin, P.V.

AU - Tretyakov, E.V.

AU - Shurikov, M.K.

AU - Votkina, D.E.

AU - Romanenko, G.V.

AU - Dmitriev, A.A.

AU - Gritsan, N.P.

AU - Ivanov, D.M.

AU - Gomila, R.M.

AU - Frontera, A.

AU - Resnati, G.

AU - Kukushkin, V.Y.

AU - Postnikov, P.S.

N1 - Export Date: 4 March 2024 CODEN: CGDEF Адрес для корреспонденции: Tretyakov, E.V.; N.D. Zelinsky Institute of Organic Chemistry, Leninsky Avenue 47, Russian Federation; эл. почта: tretyakov@ioc.ac.ru Адрес для корреспонденции: Postnikov, P.S.; Research School of Chemistry & Applied Biomedical Sciences, Lenin Avenue 30, Russian Federation; эл. почта: postnikov@tpu.ru Сведения о финансировании: Ministerio de Ciencia, Innovación y Universidades, MCIU Сведения о финансировании: Ministry of Education and Science of the Russian Federation, Minobrnauka Сведения о финансировании: Russian Science Foundation, RSF, 22-73-00077 Сведения о финансировании: European Regional Development Fund, ERDF Сведения о финансировании: Agencia Estatal de Investigación, AEI, PID2020-115637GB-I00 Текст о финансировании 1: This work was supported by the “Mega-grant” project no. 075-15-2021-585 of the Ministry of Science and Higher Education of the Russian Federation and MICIU/AEI of Spain (PID2020-115637GB-I00, FEDER funds). 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PY - 2023

Y1 - 2023

N2 - Through the interaction of a halogen bond donor (1,4-diiodotetrafluorobenzene; 1,4-FIB) with isomers of pyridyl-substituted nitronyl nitroxides (Py-NN), five novel cocrystals were constructed via halogen bonding. The cocrystals (pPy-NN)n·1,4-FIB (n = 1, 2, 4) and (mPy-NN)n·1,4-FIB (n = 1, 2) are represented by the discrete clusters Py-NN·1,4-FIB·NN-Py, cyclic tetrameric structures (pPy-NN)4·(1,4-FIB)4, or one-dimensional (1D) zigzag chains. Density functional theory calculations were used to analyze the nature of the halogen bonds and to compare the strengths of I···NPy and I···ONO interactions. The halogen bonds were shown to be quite strong, ranging from 6.4 to 9.0 kcal/mol, according to the QTAIM analysis. In addition, quantum chemical analyses revealed relatively weak exchange interactions of both ferromagnetic and antiferromagnetic nature, indicating a modulating effect of the halogen bonding on magnetic properties. These findings point to the potential usefulness of halogen bonding interactions for promoting the self-assembly of stable organic radicals for further use in the preparation of exchange-coupled organic spin systems. © 2024 American Chemical Society

AB - Through the interaction of a halogen bond donor (1,4-diiodotetrafluorobenzene; 1,4-FIB) with isomers of pyridyl-substituted nitronyl nitroxides (Py-NN), five novel cocrystals were constructed via halogen bonding. The cocrystals (pPy-NN)n·1,4-FIB (n = 1, 2, 4) and (mPy-NN)n·1,4-FIB (n = 1, 2) are represented by the discrete clusters Py-NN·1,4-FIB·NN-Py, cyclic tetrameric structures (pPy-NN)4·(1,4-FIB)4, or one-dimensional (1D) zigzag chains. Density functional theory calculations were used to analyze the nature of the halogen bonds and to compare the strengths of I···NPy and I···ONO interactions. The halogen bonds were shown to be quite strong, ranging from 6.4 to 9.0 kcal/mol, according to the QTAIM analysis. In addition, quantum chemical analyses revealed relatively weak exchange interactions of both ferromagnetic and antiferromagnetic nature, indicating a modulating effect of the halogen bonding on magnetic properties. These findings point to the potential usefulness of halogen bonding interactions for promoting the self-assembly of stable organic radicals for further use in the preparation of exchange-coupled organic spin systems. © 2024 American Chemical Society

KW - Chemical bonds

KW - Crystals

KW - Density functional theory

KW - Exchange interactions

KW - Nitrogen oxides

KW - Quantum chemistry

KW - Co-crystals

KW - Crystal packings

KW - Density-functional theory calculations

KW - Halogen bonding

KW - Halogen bonds

KW - Nitronyl nitroxides

KW - One-dimensional

KW - Pyridyl

KW - Tetrameric structures

KW - Zigzag chains

KW - Isomers

U2 - 10.1021/acs.cgd.3c01442

DO - 10.1021/acs.cgd.3c01442

M3 - статья

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

ER -