Syntheses and Characterizations of Palladium-Based Molecular Triangle/Square Compounds and Hybrid Composites with Polyoxometalates

Syntheses and characterizations of a Pd-based molecular triangle and square and hybrid composites with polyoxometalates are examined. The equilibrium between the Pd-based molecular triangle [(en*)Pd(4,4'-bpy)]3(NO3)6 and square [(en*)Pd(4,4'-bpy)]4(NO3)8 largely depends on the solvents, and both compounds have successfully been isolated: [(en*)Pd(4,4'-bpy)]3(NO3)6.3.5DMSO, monoclinic Cc (No. 9), a = 19.8210(2) A, b = 34.3667(5) A, c = 27.5484(4) A, beta = 89.9420(10) degrees , V = 18765.5(4) A3; [(en*)Pd(4,4'-bpy)]4(NO3)8, monoclinic C2/c (No. 15), a = 45.6921(16) A, b = 8.7721(8) A, c = 36.719(3) A, beta = 126.509(2) degrees , V = 11829.4(14) A3. The reactions of the Pd-based molecular triangle/square with [W6O19]2-, [W10O32]4-, and [alpha-SiW12O40]4- form [[(en*)Pd(4,4'-bpy)]4[ supersetW6O19]][W6O19]3, [[(en*)Pd(4,4'-bpy)]4[ supersetW6O19]](NO3)6, [[(en*)Pd(4,4'-bpy)]4[ supersetW10O32]][W10O32], [(en*)Pd(4,4'-bpy)]4[W10O32]2, and [(en*)Pd(4,4'-bpy)]4[alpha-SiW12O40]2. The molecular square does not encapsulate the largest [alpha-SiW12O40]4-, but it does encapsulate [W6O19]2- and [W10O32]4-. The isolation of [W6O19]2- and [alpha-SiW12O40]4- from the mixture by use of the molecular square is possible by utilizing the quite different solubility of [[(en*)Pd(4,4'-bpy)]4[ supersetW6O19]](NO3)6 and [(en*)Pd(4,4'-bpy)]4[alpha-SiW12O40]2 formed in DMSO. The size-selective encapsulation property of supramolecules may open the new way to rationalize isolation methods of the useful polyoxometalates.