Indirect detection via spin-1/2 nuclei in solid state NMR spectroscopy: Application to the observation of proximities between protons and quadrupolar nuclei

We present a comprehensive comparison of through-space heteronuclear correlation techniques for solid state NMR, combining indirect detection and single-channel recoupling method. These techniques, named D-HMQC and D-HSQC, do not suffer from dipolar truncation and can be employed to correlate quadrupolar nuclei with spin-1/2 nuclei. The heteronuclear dipolar couplings are restored under magic-angle spinning by applying supercycled symmetry-based pulse sequences (SR4₁²) or simultaneous frequency and amplitude modulation (SFAM). The average Hamiltonian theory (AHT) of these recoupling methods is developed. These results are applied to analyze the performances of D-HMQC and D-HSQC sequences. It is shown that, whatever the magnitude of spin interations, D-HMQC experiment offers larger efficiency and higher robustness than D-HSQC. Furthermore, the spectral resolution in both dimensions of proton detected two-dimensional D-HMQC and D-HSQC spectra can be enhanced by applying recently introduced symmetry-based homonuclear dipolar decoupling schemes that cause a z-rotation of the spins. This is demonstrated by ¹H- ¹³C and ¹H-²³Na correlation experiments on L-histidine and NaH₂PO₄, respectively. The two-dimensional heteronuclear ¹H-²³Na correlation spectrum yields the assignment of ²³Na resonances of NaH₂PO₄ This assignment is corroborated by first-principles calculations.