Two Extended Organic‐Inorganic Assemblies Based on Polyoxometalates and Copper Coordination Polymers with Mixed 4,4′‐Bipyridine and 2,2′‐Bipyridine Ligands

Two new organic‐inorganic hybrid compounds {Cu II 4 Cl(2,2′‐bipy) 4 (4,4′‐bipy) 3 (4,4′‐Hbipy) 2 [PMo 12 O 40 ]}[PMo 12 O 40 ] 2 · 2H 2 O ( 1 ) and [Cu I 2 (2,2′‐bipy) 2 (4,4′‐bipy)][Cu I 1.5 (2,2′‐bipy)(4,4′‐bipy)] 2 [H 3 W 12 O 40 ] ( 2 ) (2,2′‐bipy = 2,2′‐bipyridine, 4,4′‐bipy = 4,4′‐bipyridine) have been synthesised and subsequently characterised by elemental analysis, IR spectroscopy, thermal gravimetric analysis (TGA), electrochemical measurements and single‐crystal X‐ray diffraction. The most interesting feature of compound 1 is the Cu–Cl bond in the mixed ligand complex. Furthermore, 1 shows a 2D grid layered structure constructed from the [PMo 12 O 40 ] 3– polyoxoanion building units and 1D [Cu 4 (2,2′‐bipy) 4 (4,4′‐bipy) 5 Cl] n n – hybrid chains which are decorated by dangling polyoxoanion clusters that are disposed in a mutual anti orientation with respect to the layer plane. As fas as we know, compound 1 is the first characterised 2D structure with polyoxometalate clusters as pendants. Compound 2 represents the first 1D structure formed by ispolyoxotungstate building blocks [H 2 W 12 O 40 ] 6– and transition metal complex fragments with mixed ligands.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)