High-resolution indirect detection of spin-3/2 quadrupolar nuclei in solids using multiple-quantum-filtered through-space D-HMQC experiments

Abstract

Through-space heteronuclear correlation experiments under magic-angle spinning (MAS) conditions can provide unique insights into inter-atomic proximities. In particular, it has been shown that experiments based on two consecutive coherence transfers, ¹H → I → ¹H, like D-HMQC (dipolar-mediated heteronuclear multiple-quantum correlation), are usually more sensitive for the indirect detection via protons of spin-3/2 quadrupolar nuclei with low gyromagnetic ratio. Nevertheless, the resolution is often decreased by the second-order quadrupolar broadening along the indirect dimension. To circumvent this issue, we incorporate an MQMAS (multiple-quantum MAS) quadrupolar filter into the t₁ evolution period of the D-HMQC sequence, which results in a novel pulse sequence called D-HMQC-MQ. The triple-quantum coherences evolving during this filter are excited and reconverted using cosine-modulated long-pulses synchronized with the sample rotation to avoid spinning sidebands in the indirect dimension. The desired coherence transfer pathways during this sequence are selected using two nested cogwheel phase cycles with 56 steps. This high-resolution heteronuclear correlation technique is demonstrated experimentally for the indirect detection via ¹H of spin-3/2 isotopes, such as ¹¹B, ²³Na and ³⁵Cl, in zinc borate hydrate, NaH₂PO₄ and l-histidine hydrochloride, respectively. We show that this experiment can be applied at high magnetic fields up to 28.2 T for protons subject to chemical shift anisotropies larger than 20 ppm, provided the MAS frequency is sufficiently stable since the D-HMQC-MQ experiment, like the parent D-HMQC, is sensitive to MAS fluctuations, which can produce t₁-noise.