79/81Br nuclear quadrupole resonance spectroscopic characterization of halogen bonds in supramolecular assembliesElectronic supplementary information (ESI) available: 13C SSNMR spectra, powder X-ray diffractograms. See DOI: 10.1039/c8sc01094c

Despite the applicability of solid-state NMR to study the halogen bond, the direct NMR detection of 79/81 Br covalently bonded to carbon remains impractical due to extremely large spectral widths, even at ultra-high magnetic fields. In contrast, nuclear quadrupole resonance (NQR) offers comparatively sharp resonances. Here, we demonstrate the abilities of 79/81 Br NQR to characterize the electronic changes in the C-Br N halogen bonding motifs found in supramolecular assemblies constructed from 1,4-dibromotetrafluorobenzene and nitrogen-containing heterocycles. An increase in the bromine quadrupolar coupling constant is observed, which correlates linearly with the halogen bond distance ( d Br N ). Notably, 79/81 Br NQR is able to distinguish between two symmetry-independent halogen bonds in the same crystal structure. This approach offers a rapid and reliable indication for the occurrence of a halogen bond, with experimental times limited only by the observation of 79/81 Br NQR resonances. One- and two-dimensional bromine-79/81 NQR spectroscopy of halogen bond donors in a series of cocrystals shows changes in resonance frequency of up to 20 MHz and differentiates between crystallographically non-equivalent bromine sites.