Anagha Sasikumar, Jan Novotny, Jan Chyba, Libor Kobera, Radek Marek
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Supramolecular covalency of halogen bond revealed by NMR contact shift in paramagnetic cocrystals
Despite the supramolecular interactions such as halogen bonding are frequently termed "noncovalent" interactions, they have been predicted using computational methods to 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 analysis of hyperfine interactions and hyperfine shifts in NMR spectra of halogen-bonded cocrystals containing a paramagnetic transition-metal complex. We demonstrate that hyperfine interaction pertaining to the paramagnetic transition-metal center and being observed at the probed nucleus of the cocrystalized (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.
期刊介绍:
Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.