Unusual Coexistence of Nickel(II) and Nickel(IV) in the Quadruple Perovskite Ba4Ni2Ir2O12 Containing Ir2NiO12 Mixed-Metal-Cation Trimers

doi:10.1021/acs.inorgchem.8b00249

Title: Unusual Coexistence of Nickel(II) and Nickel(IV) in the Quadruple Perovskite Ba ₄Ni ₂Ir ₂O ₁₂ Containing Ir ₂NiO ₁₂ Mixed-Metal-Cation Trimers

Abstract

In this paper, the crystal chemistry and magnetic properties of two hexagonal nickel(IV)-containing perovskites, Ba ₄Ni _1.94Ir _2.06O ₁₂ and BaNiO ₃, are reported. The 12R perovskite, Ba ₄Ni _1.94Ir _2.06O ₁₂, possesses an unexpected coexistence of nickel(II) and nickel(IV). This quadruple perovskite structure contains Ir ₂NiO ₁₂ mixed-metal-cation units in which direct metal–metal bonding between nickel(IV) and iridium(V) is inferred. Finally, X-ray absorption near-edge spectroscopy and X-ray photoelectron spectroscopy measurements were conducted to confirm the simultaneous presence of nickel(II) and nickel(IV).

Authors:

Ferreira, Timothy ^[1]; Heald, Steve M. ^[2]; Smith, Mark. D. ^[1];

^[1]

Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemistry and Biochemistry
Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division, Advanced Photon Source (APS)

Publication Date:: 2018-03-02

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of South Carolina, Columbia, SC (United States)

Sponsoring Org.:: USDOE Office of Science (SC); National Science Foundation (NSF)

OSTI Identifier:: 1433915

Grant/Contract Number:: AC02-06CH11357; DMR-1301757; OIA-1655740

Resource Type:: Accepted Manuscript

Journal Name:: Inorganic Chemistry

Additional Journal Information:: Journal Volume: 57; Journal Issue: 6; Journal ID: ISSN 0020-1669

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Ferreira, Timothy, Heald, Steve M., Smith, Mark. D., and zur Loye, Hans-Conrad. Unusual Coexistence of Nickel(II) and Nickel(IV) in the Quadruple Perovskite Ba4Ni2Ir2O12 Containing Ir2NiO12 Mixed-Metal-Cation Trimers.  United States: N. p., 2018. 
        Web.  doi:10.1021/acs.inorgchem.8b00249.

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                    Ferreira, Timothy, Heald, Steve M., Smith, Mark. D., & zur Loye, Hans-Conrad. Unusual Coexistence of Nickel(II) and Nickel(IV) in the Quadruple Perovskite Ba4Ni2Ir2O12 Containing Ir2NiO12 Mixed-Metal-Cation Trimers.  United States.  doi:10.1021/acs.inorgchem.8b00249.

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                    Ferreira, Timothy, Heald, Steve M., Smith, Mark. D., and zur Loye, Hans-Conrad. Fri .  
        "Unusual Coexistence of Nickel(II) and Nickel(IV) in the Quadruple Perovskite Ba4Ni2Ir2O12 Containing Ir2NiO12 Mixed-Metal-Cation Trimers".  United States.  doi:10.1021/acs.inorgchem.8b00249.  https://www.osti.gov/servlets/purl/1433915.

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@article{osti_1433915,

  title        = {Unusual Coexistence of Nickel(II) and Nickel(IV) in the Quadruple Perovskite Ba4Ni2Ir2O12 Containing Ir2NiO12 Mixed-Metal-Cation Trimers},

  author       = {Ferreira, Timothy and Heald, Steve M. and Smith, Mark. D. and zur Loye, Hans-Conrad},

  abstractNote = {In this paper, the crystal chemistry and magnetic properties of two hexagonal nickel(IV)-containing perovskites, Ba4Ni1.94Ir2.06O12 and BaNiO3, are reported. The 12R perovskite, Ba4Ni1.94Ir2.06O12, possesses an unexpected coexistence of nickel(II) and nickel(IV). This quadruple perovskite structure contains Ir2NiO12 mixed-metal-cation units in which direct metal–metal bonding between nickel(IV) and iridium(V) is inferred. Finally, X-ray absorption near-edge spectroscopy and X-ray photoelectron spectroscopy measurements were conducted to confirm the simultaneous presence of nickel(II) and nickel(IV).},

  doi          = {10.1021/acs.inorgchem.8b00249},

  journal      = {Inorganic Chemistry},

  number       = 6,

  volume       = 57,

  place        = {United States},

  year         = {2018},

  month        = {3}

}

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DOI: 10.1021/acs.inorgchem.8b00249

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Cited by: 3 works

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Figures / Tables:

Figure 1: (Left) Polyhedral representation of Ba₄Ni_1.94Ir_2.06O₁₂ with Ni(II) shown in light green, Ni(IV) shown in dark green, Ir(V) shown in grey, Ba shown in blue and O shown in red. (Right) Local coordination environment of Ni(IV) octahedra, shown in dark green, face shared to two distorted Ir(V) octahedra, shownmore »

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Works referencing / citing this record:

CCDC 1544900: Experimental Crystal Structure Determination: JESCES : Non-CSD Structure
dataset, April 2017

Ferreira, Timothy; Heald, Steve; Smith, Mark
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1nvlhl

CCDC 1544901: Experimental Crystal Structure Determination: JESCIW : Non-CSD Structure
dataset, April 2017

Ferreira, Timothy; Heald, Steve M.; Smith, Mark. D.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1nvljm

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

Similar records in OSTI.GOV collections:

Magnetic and electrical properties of quadruple perovskites with 12 layer structures Ba{sub 4}LnM{sub 3}O{sub 12} (Ln=rare earths; M=Ru, Ir): The role of metal-metal bonding in perovskite-related oxides

Journal Article Shimoda, Yuki ; Doi, Yoshihiro ; Wakeshima, Makoto ; ... - Journal of Solid State Chemistry

Structures and magnetic and electrical properties of quadruple perovskites containing rare earths Ba{sub 4}LnM{sub 3}O{sub 12} (Ln=rare earths; M=Ru, Ir) were investigated. They crystallize in the 12L-perovskite-type structure. Three MO{sub 6} octahedra are connected to each other by face-sharing and form a M{sub 3}O{sub 12} trimer. The M{sub 3}O{sub 12} trimers and LnO{sub 6} octahedra are alternately linked by corner-sharing, forming the perovskite-type structure with 12 layers. For Ln=Ce, Pr, and Tb, both the Ln and M ions are in the tetravalent state (Ba{sub 4}Ln{sup 4+}M{sup 4+}{sub 3}O{sub 12}), and for other Ln ions, Ln ions are in the trivalentmore »« less
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Journal Article Shimoda, Yuki ; Doi, Yoshihiro ; Wakeshima, Makoto ; ... - Journal of Solid State Chemistry

New quadruple perovskite oxides Ba{sub 4}LnIr{sub 3}O{sub 12} (Ln=lanthanides) were prepared and their magnetic properties were investigated. They crystallize in the monoclinic 12L-perovskite-type structure with space group C2/m. The Ir{sub 3}O{sub 12} trimers and LnO{sub 6} octahedra are alternately linked by corner-sharing and form the perovskite-type structure with 12 layers. The Ln and Ir ions are both in the tetravalent state for Ln=Ce, Pr, and Tb compounds (Ba{sub 4}Ln{sup 4+}Ir{sub 3}{sup 4+}O{sub 12}), and for other compounds (Ln=La, Nd, Sm-Gd, Dy-Lu), Ln ions are in the trivalent state and the mean oxidation state of Ir ions is +4.33(Ba{sub 4}Ln{sup 3+}Ir{submore »« less
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Journal Article Shimoda, Yuki ; Doi, Yoshihiro ; Wakeshima, Makoto ; ... - Journal of Solid State Chemistry

Quadruple perovskites Ba{sub 4}LnRu{sub 3}O{sub 12} (Ln=La, Nd, Sm-Gd, Dy-Lu) were prepared and their magnetic properties were investigated. They adopt the 12L-perovskite-type structure consisting of Ru{sub 3}O{sub 12} trimers and LnO{sub 6} octahedra. All of these compounds show an antiferromagnetic transition at 2.5-30 K. For Ba{sub 4}NdRu{sub 3}O{sub 12}, ferrimagnetic ordering has been observed at 11.5 K. The observed magnetic transition is due to the magnetic behavior of the Ru{sup 4.33+}{sub 3}O{sub 12} trimer with S=1/2 . Magnetic properties of Ba{sub 4}LnRu{sub 3}O{sub 12} were compared with those of triple perovskites Ba{sub 3}LnRu{sub 2}O{sub 9} and double perovskites Ba{sub 2}LnRuO{submore »« less
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dataset (2)

Title: Unusual Coexistence of Nickel(II) and Nickel(IV) in the Quadruple Perovskite Ba 4Ni 2Ir 2O 12 Containing Ir 2NiO 12 Mixed-Metal-Cation Trimers

Abstract

Citation Formats

Figures / Tables:

CCDC 1544900: Experimental Crystal Structure Determination: JESCES : Non-CSD Structure dataset, April 2017

CCDC 1544901: Experimental Crystal Structure Determination: JESCIW : Non-CSD Structure dataset, April 2017

Title: Unusual Coexistence of Nickel(II) and Nickel(IV) in the Quadruple Perovskite Ba ₄Ni ₂Ir ₂O ₁₂ Containing Ir ₂NiO ₁₂ Mixed-Metal-Cation Trimers

CCDC 1544900: Experimental Crystal Structure Determination: JESCES : Non-CSD Structure
dataset, April 2017

CCDC 1544901: Experimental Crystal Structure Determination: JESCIW : Non-CSD Structure
dataset, April 2017