A simple method for the characterization of OHO-hydrogen bonds by 1H-solid state NMR spectroscopy

A set of OHO hydrogen bonded systems with known neutron diffraction structure has been studied by fast 1H-MAS echo spectroscopy. It is shown that the application of a simple rotor synchronized echo sequence combined with fast MAS allows a faithful determination of the chemical shift of the proton in the hydrogen bond. Employing the empirical valence bond order model, the experimental 1H chemical shifts of the hydrogen bonded protons are correlated to the hydrogen bond geometries. The resulting correlation between the proton chemical shift and the deviation of the proton from the center of the hydrogen bond covers a broad range of substances. Deviations from the correlation curve, which are observed in certain systems with strong hydrogen bonds, are explained in terms of proton tautomerism or delocalization in low-barrier hydrogen bonds. These deviations are a highly diagnostic tool to select potential candidates for further experimental and theoretical studies. Thus, the combination of the 1H-MAS echo sequence with the correlation curve yields a simple and versatile tool for the structural analysis of OHO hydrogen bonds. q 2004 Elsevier B.V. All rights reserved