Although supramolecular interactions such as halogen bonding are often classified as "non-covalent" interactions, computational methods have predicted that they possess a significant covalent component. In this article, we adopt a unique strategy that combines experimental solid-state NMR and relativistic DFT approaches to explore the electronic nature of previously postulated supramolecular covalency [Bora et al., Chem.-Eur. J., 2017, 23, 7315]. Our approach involves the analysis of hyperfine interactions and hyperfine shifts in the NMR spectra of halogen-bonded cocrystals containing a paramagnetic transition-metal complex. We demonstrate that the hyperfine interaction pertaining to the paramagnetic transition-metal center and observed at the probed nucleus of the cocrystallized (halogen-bonded) molecule is governed by the Fermi-contact mechanism. This contact mechanism originates in "through-bond" spin transmission and, therefore, unequivocally reports on the electron sharing between the halogen-bonded molecules, i.e., halogen-bond covalency.

CEITEC Central European Institute of Technology Masaryk University Kamenice 5 CZ 62500 Brno Czechia

Department of Chemistry Faculty of Science Masaryk University Kamenice 5 CZ 62500 Brno Czechia

Institute of Macromolecular Chemistry Czech Academy of Sciences Heyrovského nám 2 CZ 16200 Prague Czechia

National Center for Biomolecular Research Faculty of Science Masaryk University Kamenice 5 CZ 62500 Brno Czechia

Zobrazit více v PubMed

Lehn J.-M. Angew. Chem., Int. Ed. Engl. 1988;27:89–112. doi: 10.1002/anie.198800891. DOI

Webber M. J. Appel E. A. Meijer E. Langer R. Nat. Mater. 2016;15:13–26. doi: 10.1038/nmat4474. PubMed DOI

Dumele O. Chen J. Passarelli J. V. Stupp S. I. Adv. Mater. 2020;32:1907247. doi: 10.1002/adma.201907247. PubMed DOI

Geng W.-C. Jiang Z.-T. Chen S.-L. Guo D.-S. Chem. Sci. 2024;15:7811–7823. doi: 10.1039/D3SC04585D. PubMed DOI PMC

Isaacs E. D. Shukla A. Platzman P. M. Hamann D. R. Barbiellini B. Tulk C. A. Phys. Rev. Lett. 1999;82:600–603. doi: 10.1103/PhysRevLett.82.600. DOI

Luo Y. Clabbers M. T. B. Qiao J. Yuan Z. Yang W. Zou X. J. Am. Chem. Soc. 2022;144:10817–10824. doi: 10.1021/jacs.2c02426. PubMed DOI PMC

Xu Y. Szell P. M. Kumar V. Bryce D. L. Coord. Chem. Rev. 2020;411:213237. doi: 10.1016/j.ccr.2020.213237. DOI

Viger-Gravel J. Leclerc S. Korobkov I. Bryce D. L. J. Am. Chem. Soc. 2014;136:6929–6942. doi: 10.1021/ja5013239. PubMed DOI

Kolář M. H. Hobza P. Chem. Rev. 2016;116:5155–5187. doi: 10.1021/acs.chemrev.5b00560. PubMed DOI

Pell A. J. Pintacuda G. Grey C. P. Prog. Nucl. Magn. Reson. Spectrosc. 2019;111:1–271. doi: 10.1016/j.pnmrs.2018.05.001. PubMed DOI

Novotný J. Komorovsky S. Marek R. Acc. Chem. Res. 2024;57:1467–1477. doi: 10.1021/acs.accounts.3c00786. PubMed DOI PMC

Bertini I., Luchinat C., Parigi G. and Ravera E., NMR of paramagnetic molecules: applications to metallobiomolecules and models, Elsevier, 2016, vol. 2

Novotný J. Munzarová M. Marek R. Inorg. Chem. 2024;63:8580–8592. doi: 10.1021/acs.inorgchem.3c04425. PubMed DOI PMC

Malkina O. L. Lemken F. Asher J. R. Hierso J.-C. Bűhl M. Malkin V. G. Phys. Chem. Chem. Phys. 2022;24:24039–24049. doi: 10.1039/D2CP03295C. PubMed DOI

Bolla G. Sarma B. Nangia A. K. Chem. Rev. 2022;122:11514–11603. doi: 10.1021/acs.chemrev.1c00987. PubMed DOI

Cavallo G. Metrangolo P. Milani R. Pilati T. Priimagi A. Resnati G. Terraneo G. Chem. Rev. 2016;116:2478–2601. doi: 10.1021/acs.chemrev.5b00484. PubMed DOI PMC

Novák M. Foroutan-Nejad C. Marek R. Phys. Chem. Chem. Phys. 2015;17:6440–6450. doi: 10.1039/C4CP05532B. PubMed DOI

Bora P. L. Novák M. Novotný J. Foroutan-Nejad C. Marek R. Chem.–Eur. J. 2017;23:7315–7323. doi: 10.1002/chem.201700179. PubMed DOI

Novotný J. Jeremias L. Nimax P. Komorovsky S. Heinmaa I. Marek R. Inorg. Chem. 2021;60:9368–9377. doi: 10.1021/acs.inorgchem.1c00204. PubMed DOI PMC

Stilinović V. Grgurić T. Piteša T. Nemec V. Cinčić D. Cryst. Growth Des. 2019;19:1245–1256. doi: 10.1021/acs.cgd.8b01659. DOI

Rozhkov A. V. Novikov A. S. Ivanov D. M. Bolotin D. S. Bokach N. A. Kukushkin V. Y. Cryst. Growth Des. 2018;18:3626–3636. doi: 10.1021/acs.cgd.8b00408. DOI

Baerends E. J. Aguirre N. F. Austin N. D. Autschbach J. Bickelhaupt F. M. Bulo R. Cappelli C. van Duin A. C. T. Egidi F. Fonseca Guerra C. Förster A. Franchini M. Goumans T. P. M. Heine T. Hellström M. Jacob C. R. Jensen L. Krykunov M. van Lenthe E. Michalak A. Mitoraj M. M. Neugebauer J. Nicu V. P. Philipsen P. Ramanantoanina H. Rüger R. Schreckenbach G. Stener M. Swart M. Thijssen J. M. Trnka T. Visscher L. Yakovlev A. van Gisbergen S. J. Chem. Phys. 2025;162:162501. doi: 10.1063/5.0258496. PubMed DOI

Novotný J. Sojka M. Komorovsky S. Nečas M. Marek R. J. Am. Chem. Soc. 2016;138:8432–8445. doi: 10.1021/jacs.6b02749. PubMed DOI

Autschbach J. Patchkovskii S. Pritchard B. J. Chem. Theory Comput. 2011;7:2175–2188. doi: 10.1021/ct200143w. PubMed DOI

Autschbach J. Srebro M. Acc. Chem. Res. 2014;47:2592–2602. doi: 10.1021/ar500171t. PubMed DOI

Vıcha J. Novotný J. Komorovsky S. Straka M. Kaupp M. Marek R. Chem. Rev. 2020;120:7065–7103. doi: 10.1021/acs.chemrev.9b00785. PubMed DOI

Standara S. Maliňáková K. Marek R. Marek J. Hocek M. Vaara J. Straka M. Phys. Chem. Chem. Phys. 2010;12:5126–5139. doi: 10.1039/B921383J. PubMed DOI

Bader R. F. W., Atoms in Molecules: A Quantum Theory, Oxford University Press, 1990

Bader R. F. W. Stephens M. E. J. Am. Chem. Soc. 1975;97:7391–7399. doi: 10.1021/ja00859a001. DOI

Bickelhaupt F. M. and Baerends E. J., in Kohn-Sham Density Functional Theory: Predicting and Understanding Chemistry, John Wiley & Sons, Ltd, 2000, pp. 1–86

Mitoraj M. Michalak A. J. Mol. Model. 2007;13:347–355. doi: 10.1007/s00894-006-0149-4. PubMed DOI

Mitoraj M. P. Michalak A. Ziegler T. J. Chem. Theory Comput. 2009;5:962–975. doi: 10.1021/ct800503d. PubMed DOI

Wishart D. S. Sykes B. D. Richards F. M. Biochemistry. 1992;31:1647–1651. doi: 10.1021/bi00121a010. PubMed DOI

CCDC 2472007: Experimental Crystal Structure, 2025, 10.5517/ccdc.csd.cc2nzb55. DOI

CCDC 2472008: Experimental Crystal Structure, 2025, 10.5517/ccdc.csd.cc2nzb66 DOI

CCDC 2472009: Experimental Crystal Structure, 2025, 10.5517/ccdc.csd.cc2nzb77 DOI