Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba3Ln2O5Cl2

Tiglet Besara; Daniel C. Ramirez; Jifeng Sun; Nathaniel W. Falb; Wangwei Lan; Jennifer N. Neu; Jeffrey B. Whalen; David J. Singh; Theo Siegrist

doi:10.1021/acs.inorgchem.7b02265

Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba₃Ln₂O₅Cl₂

Tiglet Besara
, Daniel C. Ramirez
, Jifeng Sun
, Nathaniel W. Falb
, Wangwei Lan
, Jennifer N. Neu
, Jeffrey B. Whalen
, David J. Singh
, Theo Siegrist

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

Abstract

Single crystals of a new family of layered lanthanide oxychlorides, Ba₃Ln₂O₅Cl₂ (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. Ba₃Ln₂O₅Cl₂ phases are built up of two different blocks: a perovskite double layer of stoichiometry Ba₂Ln₂O₅ formed by corner-connected LnO₅ tetragonal bipyramids and a puckered rock-salt-like interlayer of composition BaCl₂. 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.

Original language	English
Pages (from-to)	1727-1734
Number of pages	8
Journal	Inorganic Chemistry
Volume	57
Issue number	4
DOIs	https://doi.org/10.1021/acs.inorgchem.7b02265
State	Published - Feb 19 2018
Externally published	Yes

Funding

A portion of this work was performed at the National High Magnetic Field Laboratory, which is supported by National Science Foundation Cooperative Agreement DMR-1157490 and the State of Florida. T.B., D.C.R., and T.S. acknowledge support from the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences, under Award DE-SC0008832. Work at the University of Missouri was supported by the Department of Energy through the S3TEC Energy Frontier Research Center, Award DE-SC0001299.

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title = "Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba3Ln2O5Cl2",

abstract = "Single crystals of a new family of layered lanthanide oxychlorides, Ba3Ln2O5Cl2 (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) {\AA} and c = 24.5108(7)-24.8448(9) {\AA}. Ba3Ln2O5Cl2 phases are built up of two different blocks: a perovskite double layer of stoichiometry Ba2Ln2O5 formed by corner-connected LnO5 tetragonal bipyramids and a puckered rock-salt-like interlayer of composition BaCl2. 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.",

author = "Tiglet Besara and Ramirez, \{Daniel C.\} and Jifeng Sun and Falb, \{Nathaniel W.\} and Wangwei Lan and Neu, \{Jennifer N.\} and Whalen, \{Jeffrey B.\} and Singh, \{David J.\} and Theo Siegrist",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

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doi = "10.1021/acs.inorgchem.7b02265",

language = "English",

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T1 - Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba3Ln2O5Cl2

AU - Besara, Tiglet

AU - Ramirez, Daniel C.

AU - Sun, Jifeng

AU - Falb, Nathaniel W.

AU - Lan, Wangwei

AU - Neu, Jennifer N.

AU - Whalen, Jeffrey B.

AU - Singh, David J.

AU - Siegrist, Theo

PY - 2018/2/19

Y1 - 2018/2/19

N2 - Single crystals of a new family of layered lanthanide oxychlorides, Ba3Ln2O5Cl2 (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. Ba3Ln2O5Cl2 phases are built up of two different blocks: a perovskite double layer of stoichiometry Ba2Ln2O5 formed by corner-connected LnO5 tetragonal bipyramids and a puckered rock-salt-like interlayer of composition BaCl2. 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.

AB - Single crystals of a new family of layered lanthanide oxychlorides, Ba3Ln2O5Cl2 (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. Ba3Ln2O5Cl2 phases are built up of two different blocks: a perovskite double layer of stoichiometry Ba2Ln2O5 formed by corner-connected LnO5 tetragonal bipyramids and a puckered rock-salt-like interlayer of composition BaCl2. 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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DO - 10.1021/acs.inorgchem.7b02265

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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ER -

Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba₃Ln₂O₅Cl₂

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