Two new ternary lanthanide antimony chalcogenides: Yb4Sb2S11.25 and Tm4Sb2Se11.68 containing chalcogenide Q2− and dichalcogenide (Q2)2− anions

Dark red and dark brown crystals of Yb4Sb2S11.25 and Tm8Sb4Se11.68, respectively, were obtained from the reaction of the elements in Sb2Q3 (Q=S, Se) fluxes. Both non-stoichiometric compounds are orthorhombic and crystallize in the same space group Pnnm, with two formula units per unit cell (a=12.446(2), b=5.341(1), c=12.058(2) for sulfide and a=13.126(2), b=5.623(1), c=12.499(2) for the selenide). Their crystal structures are dominated by lanthanide-chalcogenide polyhedra (CN=7 and 8), which share corners, edges, triangular- and square-faces to form a three-dimensional framework embedding antinomy cations. The latter are coordinated by three sulfide anions with 5(1+2+2) secondary contacts forming basically infinite chains running along [0 1 0]. The chalcogens in both compounds form chalcogenide Q2− and dichalcogenide (Q2)2− anionic units. The optical analysis made on those compounds shows that both are semiconductors with band gap of 1.71 and 1.22 eV for Yb4Sb2S11.25 and Tm4Sb2Se11.75, respectively.