Synthesis of giant Mo2O2S2-containing seleno-tungstate architectures: New multisite cation receptors

Abstract

Self-assembly reaction in the system containing Na2WO4, SeO32− and binuclear oxothiocation [Mo2O2(μ-S)2(H2O)6]2+ results in the formation of a nano-sized hybrid ChalcoPOM anionic complex [(W16Se2O58(H2O)2)4(W2O5)2(W4O13)2(Mo2O2(μ-S)2(H2O)2)4(Mo2O2(μ-S)2(SeO3))4]40−. The complex can be isolated as Na+/K+ salt (NaK-1) by slow evaporation of the mother liquor or Rb+ salt after addition of RbBr. Recrystallization of the Rb salt from 1 M LiCl gives red crystals of Rb17Li23[(W16Se2O58(H2O)2)4(W2O5)2(W4O13)2(Mo2O2(μ-S)2(H2O)2)4(Mo2O2(μS)2 (SeO3))4]∙120H2O (Rb-1), which was characterized by XRD, IR, TGA, and elemental analysis. Rubidium cations are encapsulated into two large cavities inside the anion which differ from the cavities in which are embedded Na+ cations.