Looking into the dynamics of molecular crystals of ibuprofen and terephthalic acid using 17O and 2H nuclear magnetic resonance analyses

Oxygen-17 and deuterium are two quadrupolar nuclei that are of interest for studying the structure and dynamics of materials by solid-state nuclear magnetic resonance (NMR). Here, O-17 and H-2 NMR analyses of crystalline ibuprofen and terephthalic acid are reported. First, improved O-17-labelling protocols of these molecules are described using mechanochemistry. Then, dynamics occurring around the carboxylic groups of ibuprofen are studied considering variable temperature O-17 and H-2 NMR data, as well as computational modelling (including molecular dynamics simulations). More specifically, motions related to the concerted double proton jump and the 180 degrees flip of the H-bonded (-COOH)(2) unit in the crystal structure were looked into, and it was found that the merging of the C=O and C-OH O-17 resonances at high temperatures cannot be explained by the sole presence of one of these motions. Lastly, preliminary experiments were performed with a H-2-O-17 diplexer connected to the probe. Such configurations can allow, among others, H-2 and O-17 NMR spectra to be recorded at different temperatures without needing to tune or to change probe configurations. Overall, this work offers a few leads which could be of use in future studies of other materials using O-17 and H-2 NMR.