Novel isopolymolybdates with different configurations of hexagram, double dish, and triangular dodecahedron

Novel isopolymolybdates [MoO3]n (1), Na8(Et4N)2[Mo12O30(SO3)2(HSO3)6]·8H2O (2), Na6(Et4N)5[Mo12O30(SO4)2(SO3)(HSO3)5]·14H2O (3) and [Mo16O52]·10NH(CH3)2 (4) were obtained and well-characterized with different configurations of hexagram, double dish and triangular dodecahedron. The hexagram-type units Mo12O36 in 1 are connected in a 3D structure with 5.7 ​Å diameter tunnels, which can adsorb a small amount of O2 (11.00 ​mg/g) at 29.9 ​bar, while no adsorption was found for H2/CH4/CO2/N2. The two coplanar {Mo6} rings in polyoxomolybdenum sulfites 2 and 3 are linked by central sodium atom to form a “double dish type” fashion. The triangular dodecahedron type of isopolymolybdate 4 consists of mixed valence [MoV3O7]4 and [MoVIO6]4 units, which are spatially arranged in the position of the vertices of the tetrahedron.