Coordination chemistry of copper-molybdates with alkoxide ligands: The {Mo 4O 10(OMe) 6} 2− and [Mo 2O 4{RC(CH 2O) 3} 2] 2− clusters as building blocks

Abstract

The reactions of the Keplerate super cluster [Mo 132O 372(CH 3CO 2) 30(H 2O) 72] 42− with a Cu(II) source and an organonitrogen donor in methanol/DMF solutions yielded a series of bimetallic organic–inorganic oxide hybrid materials, including the molecular species [Cu(phen) 2MoO 4] ( 1) and [{Cu(terpy)} 2(MoO 4) 2] ( 2) and a series of materials constructed from the tetranuclear building block {Mo 4O 10(OMe) 6} 2−: the molecular [{Cu 2(phen) 2(O 2CCH 3) 2 (MeOH)}Mo 4O 10(OMe) 6] ( 3), [{Cu(terpy)(O 2CCH 3)} 2Mo 4O 10(OMe) 6] ( 4) and [{Cu(terpy)Cl} 2Mo 4O 10(OMe) 6] ( 5), the one-dimensional phases [{Cu(bpy)(HOMe) 2}Mo 4O 10(OMe) 6] ( 6), [{Cu(bpy)(DMF) 2}Mo 4O 10(OMe) 6] ( 7), [{Cu(bpa)(DMF) 2}Mo 4O 10(OMe) 6] ( 8), [{Cu(phen)(DMF) 2}Mo 4O 10(OMe) 6] ( 9) and [{CuCl(dpa)} 2Mo 4O 10(OMe) 6] ( 10), and the two-dimensional material [{Cu 2(DMF) 2(pdpa)}{Mo 4O 10(OMe) 6} 2] ( 11). When methanol is replaced by the tridentate alkoxide tris-methoxypropane (trisp), the {Mo 2O 4(trisp) 2} 2− cluster building block is observed for [Cu(phen)Mo 2O 4(trisp) 2] ( 12), [Cu(bpa)(DMF)Mo 2O 4(trisp) 2] ( 13) and [{Cu(bpy)(NO 3)} 2Mo 2O 4(trisp) 2] ( 14).