1. Self-assembly of iodoacetylenyl-substituted nitronyl nitroxides via halogen bonding.
- Author
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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., and Postnikov, Pavel S.
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NITROXIDES , *SPIN-spin interactions , *MOLECULAR structure , *HALOGENS , *MOLECULAR crystals - Abstract
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. [ABSTRACT FROM AUTHOR]
- Published
- 2023
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