Natural abundance 15N and 13C solid-state NMR chemical shifts: high sensitivity probes of the halogen bond geometry

Paolo Cerreia Vioglio, Luca Catalano, Vera Vasylyeva, Carlo Nervi, Michele Remo Chierotti, Giuseppe Resnati, Roberto Gobetto (Corresponding Author), Pierangelo Metrangolo

    Research output: Contribution to journalArticleScientificpeer-review

    34 Citations (Scopus)


    Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a versatile characterization technique that can provide a plethora of information complementary to single crystal X-ray diffraction (SCXRD) analysis. Herein, we present an experimental and computational investigation of the relationship between the geometry of a halogen bond (XB) and the SSNMR chemical shifts of the non-quadrupolar nuclei either directly involved in the interaction (15N) or covalently bonded to the halogen atom (13C). We have prepared two series of X-bonded co-crystals based upon two different dipyridyl modules, and several halobenzenes and diiodoalkanes, as XB-donors. SCXRD structures of three novel co-crystals between 1,2-bis(4-pyridyl)ethane, and 1,4-diiodobenzene, 1,6-diiodododecafluorohexane, and 1,8-diiodohexadecafluorooctane were obtained. For the first time, the change in the 15N SSNMR chemical shifts upon XB formation is shown to experimentally correlate with the normalized distance parameter of the XB. The same overall trend is confirmed by density functional theory (DFT) calculations of the chemical shifts. 13C NQS experiments show a positive, linear correlation between the chemical shifts and the C-I elongation, which is an indirect probe of the strength of the XB. These correlations can be of general utility to estimate the strength of the XB occurring in diverse adducts by using affordable SSNMR analysis.
    Original languageEnglish
    Pages (from-to)16819–16828
    JournalChemistry - A European Journal
    Issue number47
    Publication statusPublished - 2016
    MoE publication typeA1 Journal article-refereed


    • chemical shifts
    • CPMAS
    • halogen bonding
    • NMR spectroscopy
    • normalized distance parameter


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