79/81Br nuclear quadrupole resonance spectroscopic characterization of halogen bonds in supramolecular assemblies

Cerreia Vioglio, P.; Szell, P. M.J.; Chierotti, M. R.; Gobetto, R.; Bryce, D. L.

Abstract

Despite the applicability of solid-state NMR to study the halogen bond, the direct NMR detection of 79/81Br 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 79/81Br 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 (dBr⋯N). Notably, 79/81Br 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 79/81Br NQR resonances.

Citation

Cerreia Vioglio, P., Szell, P. M., Chierotti, M. R., Gobetto, R., & Bryce, D. L. (2018). 79/81Br nuclear quadrupole resonance spectroscopic characterization of halogen bonds in supramolecular assemblies. Chemical Science, 9(20), 4555-4561. https://doi.org/10.1039/c8sc01094c

• Journal Article Type: Article
• Acceptance Date: Apr 23, 2018
• Online Publication Date: Apr 30, 2018
• Publication Date: May 28, 2018
• Deposit Date: Nov 18, 2024
• Publicly Available Date: Jan 9, 2025
• Journal: Chemical Science
• Print ISSN: 2041-6520
• Electronic ISSN: 2041-6539
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 9
• Issue: 20
• Pages: 4555-4561
• DOI: https://doi.org/10.1039/c8sc01094c
• Public URL: https://nottingham-repository.worktribe.com/output/41934167
• Publisher URL: https://pubs.rsc.org/en/content/articlelanding/2018/sc/c8sc01094c
• Additional Information: : This document is Similarity Check deposited; : Supplementary Information; : P. Cerreia Vioglio (ORCID); : P. M. J. Szell (ORCID); : M. R. Chierotti (ORCID); : R. Gobetto (ORCID); : D. L. Bryce (ORCID); : Single-blind; : Received 7 March 2018; Accepted 23 April 2018; Accepted Manuscript published 30 April 2018; Advance Article published 8 May 2018; Version of Record published 23 May 2018