Organic-inorganic hybrid materials constructed from copper-organoimine subunits and molybdoarsonate clusters

The hydrothermal reactions of MoO3, As2O5, Cu(CH3CO2)(2) . H2O and an appropriate organonitrogen ligand in the presence of HF as mineralizer yield a series of bimetallic oxides of the Cu/Mo/O/As system. The compounds [{Cu,(4,7-phen)(4,7-phenH)(2)}-Mo12AsO40] . 2.66H(2)O (1 . 2.66H(2)O) and [{Cu-3(qtpyr)(2)}Mo12AsO40] . 0.4H(2)O (2 . 0.4H(2)O) (qtpyr = 2,4':5',3",4",2'''-quaterpyridine) are two-dimensional phases constructed from Keggin clusters linked through binuclear {Cu,(4,7-phen)(4,7-Hphen)(2)}(2+) units in 1 and {Cu-3(qtpyr)(2)}(n)(3n+) metal organic networks in 2. In contrast, the structure of [{Cu-2(2,4'-Hbpy)(4)}Mo18As2O62] . 2H(2)O (3 . 2H(2)O) is one-dimensional, consisting of Dawson clusters linked through binuclear {Cu-2(Hbpy)(4)}(6+) subunits. In the case of the compounds [{Cu(5,5'-dimethyl-2,2'-bpy)}(2)Mo2O4F2(AsO4)(2)](4) and [{Cu(phen)}(2)Mo2O4F2(AsO4)(2)] (5), the fluoride mineralizer has been incorporated into the structure to give one-dimensional phases constructed from oxyfluoride {Mo2O4F2(AsO4)(2)}(2-) clusters bridged through {Cu(organonitrogen)}(2+) units. (C) 2004 Elsevier B.V. All rights reserved.