Journal of the American Chemical Society, Vol.134, No.35, 14609-14617, 2012
Variable-Temperature O-17 NMR Studies Allow Quantitative Evaluation of Molecular Dynamics in Organic Solids
We report a comprehensive variable-temperature solid-state O-17 NMR study of three O-17-labeled crystalline sulfonic adds: 2-aminoethane-1-sulfonic acid (taurine, T), 3-aminopropane-1-sulfonic acid (homotaurine, HT), and 4-aminobutane-1-sulfonic acid (ABSA). In the solid state, all three compounds exist as zwitterionic structures, NH3+-R-SO3-, in which the SO3- group is involved in various degrees of O center dot center dot center dot H-N hydrogen bonding. High-quality O-17 NMR spectra have been obtained for all three compounds under both static and magic angle spinning (MAS) conditions at 21.1 T, allowing the complete set of O-17 NMR tensor parameters to be measured. Assignment of the observed O-17 NMR parameters to the correct oxygen sites in the crystal lattice was achieved with the aid of DFT calculations. By modeling the temperature dependence of O-17 NMR powder line shapes, we have not only confirmed that the SO3- groups in these compounds undergo a 3-fold rotational jump mechanism but also extracted the corresponding jump rates (10(2)-10(5) s(-1)) and the associated activation energies (E.) for this process (E-a = 48 +/- 7, 42 +/- 3, and 45 +/- 1 kJ mol(-1) for T, HT, and ABSA, respectively). This is the first time that SO3- rotational dynamics have been directly probed by solid-state O-17 NMR. Using the experimental activation energies for SO3- rotation, we were able to evaluate quantitatively the total hydrogen bond energy that each SO3- group is involved in within the crystal lattice. The activation energies also correlate with calculated rotational energy barriers. This work provides a clear illustration of the utility of solid-state O-17 NMR in quantifying dynamic processes occurring in organic solids. Similar studies applied to selectively O-17-labeled biomolecules would appear to be very feasible.