Four novel 4f–5f heterometallic complexes could be obtained from the reaction of uranyl and lanthanide nitrates with DOTA (H4L) under hydrothermal conditions. In all cases, as in the previous examples reported, additional oxalato ligands are formed in situ. Variations in the stoichiometry of the final products and the presence of hydroxo ions in some cases appear to result in a large structural variability. In the two isomorphous complexes [(UO2)2Ln2(L)2(C2O4)] with Ln = Sm (1) or Eu (2), the lanthanide ion is located in the N4O4 site and is also bound to a carboxylate oxygen atom from a neighbouring unit, to give zigzag chains which are further linked to one another by [(UO2)2(C2O4)]2+ dications, resulting in the formation of a 3D framework. In [(UO2)4Gd2(L)2(C2O4)3(H2O)6]·2H2O (3), 2D bilayer subunits of the “double floor” type with uranyl oxalate pillars are assembled into a 3D framework by other, disordered uranyl ions. [(UO2)2Gd(L)(C2O4)(OH)]·H2O (4) is a 2D assembly in which cationic {[(UO2)2(C2O4)(OH)]+}n chains are linked to one another by the [Gd(L)]−groups. The most notable feature of this compound is the environment of the 4f ion, which is eight-coordinate and twisted square antiprismatic (TSA′), instead of nine-coordinate monocapped square antiprismatic (SA), as generally observed in DOTA complexes of gadolinium(III) and similarly-sized ions.
