Solid State NMR Techniques for Studying Hydrogen Bonded Systems

Solid State NMR Techniques for Studying Hydrogen Bonded Systems 

In principle, H NMR might be expected to be the most appropriate technique for studying both structural and dynamic aspects of hydrogen bonding in solids, by directly probing the hydrogen atoms involved in hydrogen bonds. However, it is 

When the H- H dipole-dipole interaction can be measured for a specific pair of H nuclei, studies of the temperature dependence of both the H NMR line-shape and the H NMR relaxation provide a powerful way of probing the molecular dynamics, even in very low temperature regimes at which the dynamics often exhibit quantum tunnelling behaviour. In such cases, H NMR can be superior to quasielastic neutron scattering experiments in terms of both practicality and resolution. The experimental analysis can be made even more informative by carrying out H NMR measurements on single crystal samples. In principle, studies of both the H NMR lineshape and relaxation properties can be used to derive correlation times (rc) for the motion in practice, however, spin-lattice relaxation time (T measurements are more often used to measure rc as they are sensitive to the effects of motion over considerably wider temperature ranges. 

As an example, we consider H NMR measurements on a single crystal of benzoic acid [ 14], carried out to investigate tunnelling dynamics in hydrogen bonded carboxylic acid dimers. 

For the partially deuterated benzoic acid (C6D5COOH), the solid state H NMR spectrum is dominated by the intra-dimer H- H dipole-dipole interaction. In a single crystal, both tautomers A and B are characterised by a well-defined interproton vector with respect to the direction of the magnetic field (Fig. 1). Proton motion modulates the H- H dipole-dipole interactions, which in turn affects the H NMR lineshape and the spin-lattice relaxation time. It has been shown that spin-lattice relaxation times are sensitive to the proton dynamics over the temperature range from 10 K to 300 K, and at low temperatures incoherent quantum tunnelling characterises the proton dynamics. A dipolar splitting of about 16 kHz is observed at 20 K. From the orientation dependence of the dipolar splitting, the 

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