Self-assembly of iodoacetylenyl-substituted nitronyl nitroxides via halogen bonding
Literature Information
Matvey K. Shurikov, Evgeny V. Tretyakov, Pavel V. Petunin, Darya E. Votkina, Galina V. Romanenko, Artem S. Bogomyakov, Sergi Burguera, Antonio Frontera, Vadim Yu. Kukushkin, Pavel S. Postnikov
Novel nitronyl nitroxides, namely 2-(3-iodoethynylphenyl)- and 2-(4-iodoethynylphenyl)-4,4,5,5-tetramethyl-imidazoline-3-oxyl-1-oxides, were prepared by condensation of appropriate aldehydes with 2,3-bis(hydroxylamino)-2,3-dimethylbutane followed by oxidative treatment with NaIO4. Crystal and molecular structures of the obtained paramagnets were studied by single-crystal X-ray diffraction. In the crystals, the radicals are assembled into zigzag chains in which the radical building blocks are linked by intermolecular I⋯N–O halogen bonding. Magnetic analyses revealed that in both nitronyl nitroxides, the radicals are weakly coupled. Nonetheless, spin–spin interactions in the 3-iodoethynyl isomer are antiferromagnetic, and the coupling is stronger than that in the 4-iodoethynyl derivative, in which the exchange interaction is ferromagnetic. DFT calculations in combination with MEP, NCIplot, and QTAIM analyses were used to evaluate and characterize the structure-directing halogen bonding interactions observed in the solid state of both compounds.
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