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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CrystEngComm is the forum for the design and understanding of crystalline materials. We welcome studies on the investigation of molecular behaviour within crystals, control of nucleation and crystal growth, engineering of crystal structures, and construction of crystalline materials with tuneable properties and functions. We publish hypothesis-driven research into… how crystal design affects thermodynamics, phase transitional behaviours, polymorphism, morphology control, solid state reactivity (crystal-crystal solution-crystal, and gas-crystal reactions), optoelectronics, ferroelectric materials, non-linear optics, molecular and bulk magnetism, conductivity and quantum computing, catalysis, absorption and desorption, and mechanical properties. Using Techniques and methods including… Single crystal and powder X-ray, electron, and neutron diffraction, solid-state spectroscopy, spectrometry, and microscopy, modelling and data mining, and empirical, semi-empirical and ab-initio theoretical evaluations. On crystalline and solid-state materials. We particularly welcome work on MOFs, coordination polymers, nanocrystals, host-guest and multi-component molecular materials. We also accept work on peptides and liquid crystals. All papers should involve the use or development of a design or optimisation strategy. Routine structural reports or crystal morphology descriptions, even when combined with an analysis of properties or potential applications, are generally considered to be outside the scope of the journal and are unlikely to be accepted.












![[2',6'-bis(propan-2-yloxy)-[1,1'-biphenyl]-3-yl]dicyclohexylphosphane structure [2',6'-bis(propan-2-yloxy)-[1,1'-biphenyl]-3-yl]dicyclohexylphosphane structure](https://static.chemtradehub.com/structs/787/787618-22-8-dda2.webp)

