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

Abstract

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).

Authors:
 [1];  [2];  [1]; ORCiD logo [1]
  1. Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemistry and Biochemistry
  2. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division, Advanced Photon Source (APS)
Publication Date:
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.
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. https://doi.org/10.1021/acs.inorgchem.8b00249
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. https://doi.org/10.1021/acs.inorgchem.8b00249. https://www.osti.gov/servlets/purl/1433915.
@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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Figures / Tables:

Figure 1 Figure 1: (Left) Polyhedral representation of Ba4Ni1.94Ir2.06O12 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 » in grey.« less

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Works referenced in this record:

Observation of a d-wave gap in electron-doped Sr2IrO4
journal, October 2015

  • Kim, Y. K.; Sung, N. H.; Denlinger, J. D.
  • Nature Physics, Vol. 12, Issue 1
  • DOI: 10.1038/nphys3503

Mott physics and band topology in materials with strong spin–orbit interaction
journal, March 2010

  • Pesin, Dmytro; Balents, Leon
  • Nature Physics, Vol. 6, Issue 5
  • DOI: 10.1038/nphys1606

Spin-Liquid State in the S = 1 / 2 Hyperkagome Antiferromagnet Na 4 Ir 3 O 8
journal, September 2007


Pressure Tuning of the Spin-Orbit Coupled Ground State in Sr 2 IrO 4
journal, July 2012


Spin-Orbit Physics Giving Rise to Novel Phases in Correlated Systems: Iridates and Related Materials
journal, March 2016


Crystal Structures and Characterizations of Mixed Valence 12 l -Perovskites Ba 4 EuM 3 O 12 (M = Ru and Ir)
journal, September 2009

  • Shimoda, Yuki; Doi, Yoshihiro; Wakeshima, Makoto
  • Inorganic Chemistry, Vol. 48, Issue 20
  • DOI: 10.1021/ic9009652

Low temperature structural phase transition of Ba3NaIr2O9
journal, March 2009


The crystal growth and magnetic properties of Ln2LiIrO6 (Ln=La, Pr, Nd, Sm, Eu)
journal, January 2005

  • Mugavero, Samuel J.; Smith, Mark D.; zur Loye, Hans-Conrad
  • Journal of Solid State Chemistry, Vol. 178, Issue 1
  • DOI: 10.1016/j.jssc.2004.10.033

La2.50K1.50IrO7: An example of an member of the [AnBn−1O3n][] family of perovskite-related oxides
journal, October 2005

  • Mugavero, Samuel J.; Smith, Mark D.; zur Loye, Hans-Conrad
  • Journal of Solid State Chemistry, Vol. 178, Issue 10
  • DOI: 10.1016/j.jssc.2005.07.031

Prediction of the crystal structures of perovskites using the software program SPuDS
journal, November 2001

  • Lufaso, Michael W.; Woodward, Patrick M.
  • Acta Crystallographica Section B Structural Science, Vol. 57, Issue 6
  • DOI: 10.1107/S0108768101015282

Ferromagnetism Induced by Substitution of the Iron(IV) Ion by an Unusual High-Valence Nickel(IV) Ion in Antiferromagnetic SrFeO 3
journal, December 2015

  • Seki, Hayato; Hosaka, Yoshiteru; Saito, Takashi
  • Angewandte Chemie International Edition, Vol. 55, Issue 4
  • DOI: 10.1002/anie.201509195

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