Non-stoichiometric mixed lead and tin niobates

Novel non-stoichiometric mixed lead and tin niobates with the pyrochlore structure have been synthesized via a solid-state route. The materials have been characterized by bulk chemical analysis, single-crystal and powder X-ray diffraction, 207Pb, 119Sn and 93Nb (single and triple quantum) solid-state NMR spectroscopy. The structures of the new non-stoichiometric mixed lead-tin niobate pyrochlore compounds have been Rietveld refined in the cubic system, space group Fd-3m. The steroactivity of the Sn(II) free electron pair leads to the general formula (Sn1.6-xPbx)(Nb2-ySny)O6.6-0.5y, where x (0-1.6) is the Pb(II) and y (0-0.34) is the Sn(IV) contents. 207Pb, 119Sn and (in particular) 93Nb NMR support the isomorphous substitution of tin for lead in the compounds studied. 93Nb triple-quantum magic-angle spinning NMR spectroscopy show that the materials contain, at least, two distinct niobium sites, in a 2:1 population ratio, which may be associated with different sample domains