Selective Nuclear Magnetic Resonance Method for Enhancing Long-Range Heteronuclear Correlations in Solids

The long-range heteronuclear correlation remains a significant challenge in solid-state nuclear magnetic resonance (NMR), which is critical in the structural elucidation of biomolecular, material, and pharmaceutical solids. We propose a selective NMR method, heteronuclear selective phase-optimized recoupling (hetSPR), to selectively enhance long-range correlations of interest by utilizing characteristic chemical shifts. Compared to conventional methods, hetSPR can selectively enhance desired heteronuclear correlations (e.g., ¹H-¹³C and ¹H-¹⁹F) by factors up to 5 and largely suppress the unwanted ones. The method proves useful by enhancing the long-range correlation from an intermolecular ¹H-¹⁹F distance of 4.8 Å by a factor of 2.4 in a fluorinated pharmaceutical drug, bicalutamide, under fast magic-angle spinning. It does not use selective pulses and is thus user-friendly even for nonexperts. The new method is expected to boost solid-state NMR to elucidate the structures of various solids.