The influence of fluorine spin-diffusion on 13C solid-state NMR line shapes of CF3 groups

Abstract

Indirect spin-spin couplings (“J-couplings”) lead to well-known multiplet patterns in Nuclear Magnetic Resonance (NMR) spectra that are also observable in non-decoupled solid-state NMR spectra, if the J-coupling constant exceeds the linewidth. Such J-multiplet line shapes in the solid state might however be affected by spin diffusion (SD) on the passive nuclei. When the SD rate constant is fast compared to the J-coupling constant, the multiplet resolution can be lost due to a so-called “self-decoupling” mechanism as it has been already reported in the context of decoupling and for proton SD in solid adamantane. We herein report on the influence of ¹⁹F SD on ¹³C-detected solid-state NMR spectra of a small organic molecule bearing a trifluoromethyl group. The target compound is the chiral α-(trifluoromethyl) lactic acid (TFLA). Enantiopure phases ((R) or (S), respectively) of TFLA are composed of homochiral dimers whereas the racemic phase consists of heterochiral dimers in the solid state. Despite their structural similarity, the ¹³C line shapes of the CF₃ group in cross-polarization spectra recorded at slow to medium MAS frequencies – in the range between 14.0 kHz and 60.0 kHz – differ substantially. By combining experimental observations, analytical calculation based on the Bloch-McConnell equations, and numerical spin-dynamics simulations, we demonstrate that differences in the ¹⁹F SD rate constant between racemic and enantiopure TFLA-phases significantly affect the respective solid-state ¹³C NMR spectral line shapes. Slowing down SD by increasing the magic-angle spinning frequency restores the quartet line shape for both phases of TFLA.