Hydrothermal chemistry of vanadium oxides with aromatic di- and tri-phosphonates in the presence of secondary metal copper(II) cationic complex subunits

The hydrothermal chemistry of the copper-organonitrogen ligand/vanadium oxide/aromatic phosphonate system has been studied. Not only was HF required to induce crystallization, but product composition was highly dependent on the HF/V ratio of the reactions. At relatively low concentrations of HF/V of 6:1, materials of the Cu(II)-ligand/VxOy/organophosphonate type were observed, namely, [{Cu(phen)}(2)V2O5(O3PC6H4PO3)] (1), [Cu(phen)VO2(HO3PC6H4PO3)] (2), [{Cu(terpy)}(2)V2O5 (O3PC6H4PO3)] (3), [{Cu(phen)(H2O)}VO2(HO3PC6H4PO3)] (6), [{Cu(phen)}VO2(HO3PC6H4PO3)] (7a and 7b), [Cu(C5H4NCO2)(2)V2O4(HO3PC6H4POH3)] (8), [Cu(bpy)VO2 {(HO3P)(3)C6H3}]center dot 1.5H(2)O (12 center dot 1.5H(2)O), [{Cu(bpy)}(2)V3O7{(O3P)(2)C6H3PO3H}] (13) and [Cu(phen)V3O6(H2O){(O3P)(2)C6H3 (PO3H)}] (14). When the HF concentration was raised, materials incorporating fluoride anion were observed; that is, compounds of the Cu(II)-ligand/VxOyFz/organophosphonate type: [{Cu(bpa)}(2)VO2F(H2O)(O3PC6H4PO3)]center dot H2O (4), [{Cu(bpa)}(2)V2O4F2(O3PC6H4PO3)] (5), [{Cu(bpy)}(2)V2O4F2(O3PC6H4PO3)] (9), [{Cu(terpy)}(2)V3O6F(HO3PC6H4PO3)(2)] (10), [{Cu(bpa)}(2)V2O4F2(O3PC6H4PO3)] (11). At HF/V concentrations of 25:1 or greater, vanadium free products, Cu(II) ligand/organophosphonate, were obtained: [Cu(C5H4NCO2)(2)(H2O3PC6H4PO3H2)]center dot H2O (15 center dot H2O), [Cu(C5H4NCO2)(2)(H2O3PC6H4PO3H2)] (16), [Cu(bpy)(H2O){(HO3P)(2)C6H3(PO3H2)}] (17), [Cu(bpy){(HO3P)(2)C6H3(PO3H2)}]center dot H2O (18 center dot H2O), [Cu(phen){(H2O3P)C6H3(PO3H)(2)}]center dot 2H(2)O (19 center dot 2H(2)O) and [Cu(bpa){H2O3PC6H3(PO3H)(2)}]center dot H2O (20 center dot H2O). The structural chemistry is unusually diverse with the Cu(II) ligand/VxOy/organophosphonate series exhibiting one-, two- and three-dimensional structures with a variety of copper-vanadate and vanadophosphonate substructures. The structural chemistry is discussed in relation o other examples of materials of the Cu(II) ligand/VxOy/organophosphonate and Cu(II) ligand/VxOyFz/organophosphonate families.