Open AccessSynthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba3Ln2O5Cl2
Author(s) -
Tiglet Besara,
Daniel Candala Ramírez,
Jifeng Sun,
Nathaniel W. Falb,
Wangwei Lan,
Jennifer Neu,
Jeffrey B. Whalen,
David J. Singh,
Theo Siegrist
Publication year - 2018
Publication title -
inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 233
eISSN - 1520-510X
pISSN - 0020-1669
DOI - 10.1021/acs.inorgchem.7b02265
Subject(s) - lanthanide , chemistry , tetragonal crystal system , crystallography , valence (chemistry) , stoichiometry , crystal structure , lanthanide contraction , atomic orbital , density functional theory , lattice energy , barium , electronic band structure , inorganic chemistry , computational chemistry , condensed matter physics , ion , physics , organic chemistry , quantum mechanics , electron
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 etragonal 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. The synthesis of this family suggests a route to other potential multianion phases.
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