Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba 3 Ln 2 O 5 Cl 2
Single crystals of a new family of layered lanthanide oxychlorides, Ba 3 Ln 2 O 5 Cl 2 (Ln = Gd–Lu), have been synthesized from a molten barium flux. This family crystallizes in the space group I4/ mmm (No. 139; Z = 2) with lattice parameters a = 4.3384(1)–4.4541(1) Å and c = 24.5108(7)–24.8448(9) Å. Ba 3 Ln 2 O 5 Cl 2 phases are built up of two different blocks: a perovskite double layer of stoichiometry Ba 2 Ln 2 O 5 formed by corner-connected LnO 5 tetragonal bipyramids and a puckered rock-salt-like interlayer of composition BaCl 2 . A complete structural study along with bond-valence-sum calculations shows that, for lanthanides larger than gadolinium, the structure becomes unstable. Density functional theory calculations show that the valence-band edge is dominated by oxygen orbitals, whereas the conduction band forms from Ba 5d orbitals. Finally, the synthesis of this family suggests a route to other potential multianion phases.