Discovery of two Na+-centered Silverton-type polyoxometalates {NaM12O42} (M = Mo, W).

Two new members of highly charged Silverton archetype [NaM₁₂O₄₂]¹¹⁻ were demonstrated in the 3D POM-based frameworks Na₃[NaM₁₂O₄₂(Ru(DMSO)₃)₄]·13H₂O (M = Mo (1), W (2)), where the unusual icosahedron coordination of a Na⁺ ion incubated as a heteroatom is reported for the first time in topical POMs. Furthermore, ²³Na NMR was applied to certify the interpretation of X-ray diffraction data concerning Na localization. Additionally, the porous nature of the frameworks 1 and 2 has also been investigated. [ABSTRACT FROM AUTHOR]