Pentavalent and tetravalent uranium selenides, Tl3Cu4USe6 and Tl2Ag2USe4: syntheses, characterization, and structural comparison to other layered actinide chalcogenide compounds

The compounds Tl(3)Cu(4)USe(6) and Tl(2)Ag(2)USe(4) were synthesized by the reaction of the elements in excess TlCl at 1123 K. Both compounds crystallize in new structure types, in space groups P2(1)/c and C2/m, respectively, of the monoclinic system. Each compound contains layers of USe(6) octahedra and MSe(4) (M = Cu, Ag) tetrahedra, separated by Tl(+) cations. The packing of the octahedra and the tetrahedra within the layers is compared to the packing arrangements found in other layered actinide chalcogenides. Tl(3)Cu(4)USe(6) displays peaks in its magnetic susceptibility at 5 and 70 K. It exhibits modified Curie-Weiss paramagnetic behavior with an effective magnetic moment of 1.58(1) μ(B) in the temperature range 72-300 K, whereas Tl(2)Ag(2)USe(4) exhibits modified Curie-Weiss paramagnetic behavior with μ(eff) = 3.4(1) μ(B) in the temperature range 100-300 K. X-ray absorption near-edge structure (XANES) results from scanning transmission X-ray spectromicroscopy confirm that Tl(3)Cu(4)USe(6) has Se bonding characteristic of discrete Se(2-) units, Cu bonding generally representative of Cu(+), and U bonding consistent with a U(4+) or U(5+) species. On the basis of these measurements, as well as bonding arguments, the formal oxidation states for U may be assigned as +5 in Tl(3)Cu(4)USe(6) and +4 in Tl(2)Ag(2)USe(4).