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.