Uranyl and/or Rare-Earth Mellitates in Extended Organic–Inorganic Networks: A Unique Case of Heterometallic Cation–Cation Interaction with UVI═O–LnIII Bonding (Ln = Ce, Nd)

Abstract

A series of uranyl and lanthanide (trivalent Ce, Nd) mellitates (mel) has been hydrothermally synthesized in aqueous solvent. Mixtures of these 4f and 5f elements also revealed the formation of a rare case of lanthanide-uranyl coordination polymers. Their structures, determined by XRD single-crystal analysis, exhibit three distinct architectures. The pure lanthanide mellitate Ln(2)(H(2)O)(6)(mel) possesses a 3D framework built up from the connection of isolated LnO(6)(H(2)O)(3) polyhedra (tricapped trigonal prism) through the mellitate ligand. The structure of the uranyl mellitate (UO(2))(3)(H(2)O)(6)(mel)·11.5H(2)O is lamellar and consists of 8-fold coordinated uranium atoms linked to each other through the organic ligand giving rise to the formation of a 2D 3(6) net. The third structural type, (UO(2))(2)Ln(OH)(H(2)O)(3)(mel)·2.5H(2)O, involves direct oxygen bondings between the lanthanide and uranyl centers, with the isolation of a heterometallic dinuclear motif. The 9-fold coordinated Ln cation, LnO(5)(OH)(H(2)O)(3), is linked to the 7-fold coordinated uranyl (UO(2))O(4)(OH) (pentagonal bipyramid) via one μ(2)-hydroxo group and one μ(2)-oxo group. The latter is shared between the uranyl bonding (U═O = 1.777(4)/1.779(6) Å) and a long Ln-O bonding (Ce-O = 2.822(4) Å; Nd-O = 2.792(6) Å). This unusual linkage is a unique illustration of the so-called cation-cation interaction associating 4f and 5f metals. The dinuclear motif is then further connected through the mellitate ligand, and this generates organic-inorganic layers that are linked to each other via discrete uranyl (UO(2))O(4) units (square bipyramid), which ensure the three-dimensional cohesion of the structure. The mixed U-Ln carboxylate is thermally decomposed from 260 to 280 °C and then transformed into the basic uranium oxide (U(3)O(8)) together with U-Ln oxide with the fluorite structural type ("(Ln,U)O(2)"). At 1400 °C, only fluorite type "(Ln,U)O(2)" is formed with the measured stoichiometry of U(0.63)Ce(0.37)O(2) and U(0.60)Nd(0.40)O(2-δ).