Self-assembly of iodoacetylenyl-substituted nitronyl nitroxides <i>via</i> halogen bonding

Shurikov, Matvey K.; Tretyakov, Evgeny V.; Petunin, Pavel V.; Votkina, Darya E.; Romanenko, Galina V.; Bogomyakov, Artem S.; Burguera, Sergi; Frontera, Antonio; Kukushkin, Vadim Yu.; Postnikov, Pavel S.

doi:10.1039/d3ce00735a

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“…XB was also used as a structure-directing interaction in crystalline dithiadiazolyl radicals . For instance, a search in the Cambridge Structural Database (CSD version 5.42) revealed 21 structures (parameters of search are listed in the experimental part) of nitroxide-containing crystals featuring short contacts whose geometric parameters are similar to those required for XB. − Most of these structures have never been analyzed from the viewpoint of XB-based structure-directing interactions, and only a few papers have addressed applications of XB to the design of multispin architectures (Figure ). − …”

Section: Introductionmentioning

confidence: 99%

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

Petunin,

Tretyakov,

Shurikov

et al. 2024

Crystal Growth & Design

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Through the interaction of a halogen bond donor (1,4-diiodotetrafluorobenzene; 1,4-FIB) with isomers of pyridylsubstituted 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.

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