Probing ²⁹Si-¹⁷O connectivities and proximities by solid-state NMR

The measurement of dipolar and J- couplings between ²⁹Si and ¹⁷O isotopes is challenging owing to (i) the low abundance of both isotopes and (ii) their close Larmor frequencies, which only differ by 19%. These issues are circumvented here by the use of isotopic enrichment and dedicated triple-resonance magic-angle spinning NMR probe. The surface of ²⁹Si-enriched silica was labelled with ¹⁷O isotope and heated at 80 and 200 °C. ²⁹Si-¹⁷O connectivities and proximities were probed using two-dimensional (2D) through-bond and through-space heteronuclear multiple-quantum coherences (J- and D-HMQC) experiments between ¹⁷O and ²⁹Si nuclei. The simulation of the build-up of the J- and D-HMQC signals allowed the first experimental measurement of J- and dipolar coupling constants between ¹⁷O and ²⁹Si nuclei. These HMQC experiments allow distinguishing two distinct siloxane (SiOSi) oxygen sites: (i) those covalently bonded to Q³ and Q⁴ groups, having a hydroxyl group as a second neighbour and (ii) those covalently bonded to two Q⁴ groups. The measured J- and dipolar coupling constants of siloxane ¹⁷O nucleus with Q^{4 29}Si nuclei differ from those with Q^{3 29}Si nuclei. These results indicate that the ²⁹Si-¹⁷O one-bond J-coupling and Si-O bond length depend on the second neighbours of the Si atoms.