Recent advances in solid-state NMR spectroscopy of quadrupolar nuclei

Nuclear magnetic resonance (NMR) spectroscopy of quadrupolar nuclei (i.e., those with a spin quantum number I > 1/2) has always been viewed as “difficult” owing to the presence of an anisotropic broadening arising from the interaction of the nuclear electric quadrupole moment with the electric field gradient. This quadrupolar interaction can be considerable, resulting in broadening of the spectral resonances often over many MHz. Furthermore, magic-angle spinning (MAS), a conventional approach for increasing the resolution in solid-state NMR, is often unable to remove the broadening completely and high-resolution spectra are generally not obtained. Despite the vast amount of information contained in the anisotropic linewidths and lineshapes, the resolution and sensitivity challenges have, until recently, somewhat limited the application of solid-state NMR for quadrupolar nuclei. In general, structural information, such as that obtained through recoupling techniques or from two-dimensional correlation spectroscopy, is much more difficult to extract easily and accurately. However, recent advances in magnet design, probe hardware and pulse sequence development have significantly improved the ease with which quadrupolar spins can be studied and high-resolution spectra can be obtained, and recent applications are beginning to exploit the wealth of information available. In this discussion, we highlight just a few of the recent developments in this area, including new state-of-the art correlation experiments, the expanding study of nuclei with low gyromagnetic ratio, γ, the increasing application of first-principles calculations in the solid state, and methods which exploit the quadrupolar broadening to provide information on dynamics. Whilst not a complete review, it is hoped that this brief overview of some of the more exciting recent developments can provide insight into the challenges, and the rewards, involved in the NMR study of quadrupolar nuclei.