Assembly of organic–inorganic hybrid supramolecular materials based on {P2W18O62}6− anion and Cu(ii)/Mn(ii) complex

Abstract

Six novel hybrids based on Wells–Dawson polyoxometalates, [{Cu_0.5(imi)(O_0.5H)Cu_0.5(imi)₂}₂{Cu_0.5(imi)}₂(P₂W₁₈O₆₂)]·5H₂O (1), (Himi)₂[{Mn(2,2′-bpy)₂}₂(P₂W₁₈O₆₂)]·H₂O (2), (Himi)₂[{Cu(2,2′-bpy)₂}₂(P₂W₁₈O₆₂)]·H₂O (3), [Cu(phen)₂Cl]₂[{Cu(phen)(H₂O)(gly)Cu(phen)}(P₂W₁₈O₆₂)]·3H₂O (4) [Mn(phen)₃][{Mn(phen)₂(H₂O)}₂(P₂W₁₈O₆₂)]·3.5H₂O (5), and (H₂phen)[Mn(phen)₃][{Mn(phen)(H₂O)₃}(P₂W₁₈O₆₂)]·3.5H₂O (6), (imi = imidazole, bpy = bipyridine, phen = 1,10-phenanthroline, gly = glycine), have been synthesized under hydrothermal conditions and structurally characterized by elemental analysis, IR, UV, TG, and single-crystal X-ray diffraction. Compound 1 represents an unprecedented 2D metal–organic layer based on hexad-supported {P₂W₁₈O₆₂}⁶⁻ (abbreviated to P₂W₁₈) anions and Cu–imi complexes linker. Compounds 2 and 3 exhibit similar 1-D chains. Compound 4 displays a 1-D chain built by {P₂W₁₈} clusters and an unusual binuclear complex {Cu(phen)(H₂O)(gly)Cu(phen)} linker. Compounds 5 and 6 are bi-supported and mono-supported 0-D clusters. All the clusters are further packed into various 3-D assemblies via strong hydrogen-bonding and supramolecular interactions. Furthermore, electrochemical behavior and magnetic properties of 1–6 have been investigated in detail.