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.