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Issue 31, 2014
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Probing halogen bonds with solid-state NMR spectroscopy: observation and interpretation of J(77Se,31P) coupling in halogen-bonded P[double bond, length as m-dash]Se⋯I motifs

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Abstract

Halogen bonds constitute an important and topical class of non-covalent interaction. We report a combined X-ray diffraction, multinuclear (77Se, 31P, 13C) solid-state magnetic resonance, and computational study of a series of crystalline triphenylphosphine selenide–iodoperfluorobenzene complexes which feature P[double bond, length as m-dash]Se⋯I–C halogen bonds. Selenium-77 chemical shifts increase due to halogen bonding with iodine and correlate with the P[double bond, length as m-dash]Se distance, which in turn correlates with the strength of the halogen bond. J(77Se,31P) coupling constants increase in magnitude as the halogen bond weakens. This observation is understood via a natural localized molecular orbital (NLMO) DFT approach which shows that contributions from the selenium lone pair orbital tend to dominate both the magnitude and trends in J(77Se,31P), with the selenium–phosphorus bonding orbital being the second largest contributor. This work suggests that J couplings measured via NMR spectroscopy may play an important role in the characterization of halogen bonds, in clear analogy with their role in the characterization of hydrogen bonds.

Graphical abstract: Probing halogen bonds with solid-state NMR spectroscopy: observation and interpretation of J(77Se,31P) coupling in halogen-bonded P [[double bond, length as m-dash]] Se⋯I motifs

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Publication details

The article was received on 17 Feb 2014, accepted on 20 Mar 2014 and first published on 23 Apr 2014


Article type: Paper
DOI: 10.1039/C4CE00345D
Author version available: Download Author version (PDF)
Citation: CrystEngComm, 2014,16, 7285-7297
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    Probing halogen bonds with solid-state NMR spectroscopy: observation and interpretation of J(77Se,31P) coupling in halogen-bonded P[double bond, length as m-dash]Se⋯I motifs

    J. Viger-Gravel, J. E. Meyer, I. Korobkov and D. L. Bryce, CrystEngComm, 2014, 16, 7285
    DOI: 10.1039/C4CE00345D

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