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 [{Cu2(4,7-phen)(4,7-phenH)2}Mo12AsO40] · 2.66H2O (1 · 2.66H2O) and [{Cu3(qtpyr)2}Mo12AsO40] · 0.4H2O (2 · 0.4H2O) (qtpyr = 2,4′:5′, 3″:4″,2‴-quaterpyridine) are two-dimensional phases constructed from Keggin clusters linked through binuclear {Cu2(4,7-phen)(4,7-Hphen)2}2+ units in View the MathML source1and{Cu3(qtpyr)2}n3n+ metal organic networks in 2. In contrast, the structure of [{Cu2(2,4′-Hbpy)4}Mo18As2O62] · 2H2O (3 · 2H2O) is one-dimensional, consisting of Dawson clusters linked through binuclear {Cu2(Hbpy)4}6+ subunits. In the case of the compounds [{Cu(5,5′-dimethyl-2,2′-bpy)}2Mo2O4F2(AsO4)2] (4) and [{Cu(phen)}2Mo2O4F2(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.