Blind spheres of paramagnetic dopants in solid state NMR

Solid-state NMR on paramagnetically doped crystal structures gives information about the spatial distribution of dopants in the host. Paramagnetic dopants may render NMR active nuclei virtually invisible by relaxation, paramagnetic broadening or shielding. In this contribution blind sphere radii r0 are reported, which could be extracted through fitting the NMR signal visibility function f(x) = exp(-a r03x) to experimental data obtained on several model compound series: La1-xLnxPO4 (Ln = Nd, Sm, Gd, Dy, Ho, Er, Tm, Yb), Sr1-xEuxGa2S4 and (Zn1-xMnx)3(PO4)2·4H2O. Radii were extracted for 1H, 31P and 71Ga, and dopants like Nd3+, Gd3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+ and Mn2+. The observed radii determined differed in all cases and covered a range from 5.5 to 13.5 A. While these radii were obtained from the amount of invisible NMR signal, we also show how to link the visibility function to lineshape parameters. We show under which conditions empirical correlations of linewidth and doping concentration can be used to extract blind sphere radii from second moment or linewidth parameter data. From the second moment analysis of La1-xSmxPO431P MAS NMR spectra for example, a blind sphere size of Sm3+ can be determined, even though the visibility function remains close to 100% over the entire doping range. Dependence of the blind sphere radius r0 on the NMR isotope and on the paramagnetic dopant could be suggested and verified: for different nuclei, r0 shows a 3√γ-dependence, γ being the gyromagnetic ratio. The blind sphere radii r0 for different paramagnetic dopants in a lanthanide series could be predicted from the pseudo-contact coupling.