pH-Controlled One Pot Syntheses of Giant Mo2O2S2-Containing Seleno-Tungstate Architectures.

Self-assembly reactions of Na2WO4, SeO2/SeO32-, and [Mo2O2(μ-S)2(H2O)6]2+ give, depending on the pH value, two new large polyoxometalate complexes: i.e., [(γ-Se2W14O52)3(Mo2O2(μ-S)2(H2O)2)6]24- (1) isolated at pH 3.5 and [(γ-Se2W14O52)4(WO3(H2O))8(W2O5)2(W4O12)2(Mo2O2(μ-S)2(H2O)2)4(Mo2O2(μ-S)2(SeO3))4]36- (2) isolated at pH 2. Both compounds were characterized in the solid state by single-crystal X-ray diffraction, EDX, elemental analysis, TGA, and FT-IR and in solution by ESI-MS and NMR.