Influence of proton coupling on symmetry-based homonuclear (19)F dipolar recoupling experiments

Abstract

We study the efficiency of two symmetry based homonuclear (19)F double-quantum recoupling sequences for moderate (R142(6)) and ultra-fast (R144(5)) MAS under the influence of strong (1)H-(1)H and (1)H-(19)F dipolar interactions and (1)H continuous wave decoupling. Simulations based on various spin systems derived from the organic solid 1,3,5-tris(2-fluoro-2-methylpropionylamino)benzene (F-BTA), used as a model system, reveal that the strong-decoupling limit is not accessible even for moderate spinning speeds. Additionally, for the no-decoupling limit improved DQ efficiencies are predicted for both moderate and ultra-fast MAS. Strong perturbations of build-up curves can be avoided by additional stabilisation through supercycling. Additional (1)H cw decoupling during (19)F recoupling rapidly reduces the maximum DQ efficiency when deviating from the no-decoupling limit. These effects were confirmed by experimental data on F-BTA. For moderate spinning the influence of (1)H-(1)H and (1)H-(19)F couplings is markedly stronger compared to ultra-fast MAS. For the latter case those influences reduce to a constant scaling if only short excitation times up to the first minimum are taken into account. Based on this analysis the experimental build-up curves of 1,3,5-tris(2-fluoro-2-methylpropionylamino)benzene can be refined with homonuclear (19)F spin systems which allow to probe even subtle structural differences for the fluorine atoms of F-BTA.

Keywords: 19F homonuclear DQ recoupling; 1H decoupling; Solid-state NMR spectroscopy; Symmetry based dipolar recoupling.