Quantifying the quadrupolar interaction by 45Sc-NMR spectroscopy of single crystals

Single crystals of the compound [${\left\{Sc{\left(H_{2}O\right)}_5\left(\mu -OH\right)\right\}}_2$]Cl₄ ⋅ 2H₂O were studied by ⁴⁵Sc-NMR, with the effect of the quadrupolar coupling interaction on the spectra of the spin-7/2 nucleus analysed in the hierarchical framework of perturbation theory. Orientation-dependent spectra acquired at B₀ = 17.6 T showed strong second-order effects due to the comparatively large coupling constant of χ = |14.613 ± 0.006| MHz, with an associated asymmetry parameter of η_Q = 0.540 9 ± 0.000 4. By analysing the splittings of the ±3/2 satellites, which in good approximation are subjected to first-order effects only, the full quadrupolar coupling tensor could be determined. The second-order effects caused by this tensor were calculated according to theoretical predictions for all orientations, and subtracted from both the centres of gravity of the satellites, and the central transitions. This allowed extraction of the full chemical shift tensor, with the eigenvalues being δ₁₁ = (5.6 ± 0.9) ppm, δ₂₂ = (12.4 ± 0.9) ppm, and δ₃₃ = (38.5 ± 0.9) ppm. In spectra acquired at a lower magnetic field of B₀ = 9.4 T, third-order effects could be detected, and similarly quantified using analytical expressions.