Three new multidimensional organic–inorganic hybrids based on polyoxometalates and copper coordination polymers with 4,4′-bipyridine ligands

Three new organic–inorganic hybrid materials with 4,4′-bipy ligands and copper cations as linkers, [CuII(H2O)(4,4′-bipy)2][CuII(H2O)(4,4′-bpy)2]2H[CuIIP8Mo12O62H12] · 5H2O (1), [CuI(4,4′-bipy)][CuII(4,4′-bipy)]2 (BW12O40) · (4,4′-bipy) · 2H2O (2) and [CuI (4,4′-bipy)]3 (PMo12O40) · (pip) · 2H2O (3) (pip = piperazine; 4,4′-bipy = 4,4′-bipyridine), have been hydrothermally synthesized. The single X-ray structural analysis reveals that the structure of 1 is constructed from [Cu(H2O)(4,4′-bipy)2] complexes into a novel, three-dimensional supermolecular network with 1-D channels in which Cu[P4Mo6]2 dimer clusters reside. To the best of our knowledge, compound 1 is the first complex in which the [P4Mo6] clusters have been used as a non-coordinating anionic template for the construction of a novel, three-dimensional supermolecular network. Compound 2 is constructed from the six-supported [BW12O40]5− polyoxoanions and [CuI(4,4′-bipy)] and [CuII(4,4′-bipy)] groups into a novel, 3-D network. Compound 3 exhibits unusual 3-D supramolecular frameworks, which are constructed from tetrasupporting [PMo12O40]3− clusters and [CuI (4,4′-bipy)n] coordination polymer chains. The electrochemical properties of 2 and 3 have been investigated in detail.