FRAMEWORK MATERIALS CONTAINING POLYOXOVANADATES AS BUILDING UNITS: SYNTHESIS AND CHARACTERIZATION OF (N_2H_5)_2[M_3(H_2O)_(12)V_(18)O_(42)(EO_4)] centre dot 24H_2O(M = Mg, Ca) AND Li_6[Mn_3(H_2O)_(12)V_(18)O_(42)(EO_4)] centre dot 24H_2O (E = V, S)

摘要

The reaction of an aqueous solution of lithium vanadate with hydrazinium sulfate results in a dark-colored solution that reacts with magnesium sulfate heptahydrate, calcium sulfate dihydrate, and manganese(II) chloride tetrahydrate to yield single crystals of (N_2H_5)_2[M_3(H_2O)_(12)V_(18)O_(42)(EO_4)] centre dot 24H_2O (M = Mg, Ca) and Li_6[Mn_3(H_2O)_(12)V_(18)O_(42)(EO_4)] centre dot 24H_2O (E = V, S), respectively. The crystal structures of the new solids consist of interpenetrating three-dimensional networks of {V_(18)O_(42)EO_4)} clusters interlinked via bridging {M(H_2O)_4} (M = Mg, Ca, Mn) groups. The voids in these structures are occupied by lattice water and ion exchangeable cations.