Synthesis, structures and properties of new hybrid solids containing ruthenium complexes and polyoxometalates

Two new organic–inorganic hybrid solids containing Keggin ions and ruthenium complexes have been synthesized and characterized by FT-IR, UV–vis, luminescence, X-ray, and TG analysis. In KNa[Ru(bpy)3]2[H2W12O40]·8H2O (1), the [Ru(bpy)3]2+ (bpy=2,2′-bipyridine) complex ions are located in between the infinite one-dimensional double-chains formed by adjacent Keggin anions [H2W12O40]6− linked through {KO7} and {NaO6} polyhedra, while in K6[Ru(pzc)3]2[SiW12O40]•12H2O (2), the [Ru(pzc)3]− (pzc=pyrazine-2-carboxylate) complex anions are confined by layered networks of the [SiW12O40]4− clusters connected by potassium ions. Both compounds exhibit three-dimensional frameworks through noncovalent interactions such as hydrogen bonds and anion⋯π interactions. Additionally, compound 1 shows strong luminescence at 604 nm in solid state at room temperature.