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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 Laboratory (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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Cited by: 7 works
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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 coupling in iridium-based 5 d compounds probed by x-ray absorption spectroscopy
journal, November 2012


Tuning Magnetic Coupling in Sr 2 IrO 4 Thin Films with Epitaxial Strain
journal, April 2014


New material for probing spin-orbit coupling in iridates
journal, April 2015


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


Structure and Properties of Ir-Containing Oxides with Large Spin–Orbit Coupling: Ba 2 In 2– x Ir x O 5+δ
journal, March 2016


Synthesis, Structure, and Unexpected Magnetic Properties of La 3 Re 2 O 10
journal, September 2007

  • Cuthbert, Heather L.; Greedan, John E.; Vargas-Baca, Ignacio
  • Inorganic Chemistry, Vol. 46, Issue 21
  • DOI: 10.1021/ic701011r

Synthesis, Crystal Structures, and Magnetic Properties of New 12L-Perovskites Ba 4 LnRu 3 O 12 (Ln = Lanthanides)
journal, July 2008

  • Shimoda, Yuki; Doi, Yoshihiro; Hinatsu, Yukio
  • Chemistry of Materials, Vol. 20, Issue 13
  • DOI: 10.1021/cm800708g

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

Complex 5d Magnetism in a Novel S = 1/2 Trimer System, the 12L Hexagonal Perovskite Ba 4 BiIr 3 O 12
journal, October 2013

  • Miiller, Wojciech; Dunstan, Matthew T.; Huang, Zixin
  • Inorganic Chemistry, Vol. 52, Issue 21
  • DOI: 10.1021/ic4014619

Structural Predictions in the ABO3 Phase Diagram
journal, April 1994

  • Giaquinta, Daniel M.; zur Loye, Hans-Conrad
  • Chemistry of Materials, Vol. 6, Issue 4
  • DOI: 10.1021/cm00040a007

Synthesis, Structure, and Magnetic Properties of Sr2NiOsO6 and Ca2NiOsO6:  Two New Osmium-Containing Double Perovskites
journal, November 2005

  • Macquart, René; Kim, Seung-Joo; Gemmill, William R.
  • Inorganic Chemistry, Vol. 44, Issue 26
  • DOI: 10.1021/ic051045+

Flux growth and characterization of Sr2NiWO6 single crystals
journal, July 2015


Crystal growth, structure and magnetic properties of the double perovskites Ln2MgIrO6 (Ln=Pr, Nd, Sm–Gd)
journal, February 2010

  • Mugavero III, Samuel J.; Fox, Adam H.; Smith, Mark D.
  • Journal of Solid State Chemistry, Vol. 183, Issue 2
  • DOI: 10.1016/j.jssc.2009.11.025

Low temperature structural phase transition of Ba3NaIr2O9
journal, March 2009


Nd 2 K 2 IrO 7 and Sm 2 K 2 IrO 7 : Iridium(VI) Oxides Prepared under Ambient Pressure
journal, November 2008

  • Mugavero, Samuel J.; Smith, Mark D.; Yoon, Won-Sub
  • Angewandte Chemie International Edition, Vol. 48, Issue 1
  • DOI: 10.1002/anie.200804045

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

The magnetic properties of iridium in mixed-metal oxides
journal, November 1993


Novel Mixed-Valent (V/VI) Triple Perovskite Ruthenates:  Observation of a Complex Low-Temperature Structural and Magnetic Transition
journal, November 2002

  • Stitzer, Katharine E.; Smith, Mark D.; Gemmill, William R.
  • Journal of the American Chemical Society, Vol. 124, Issue 46
  • DOI: 10.1021/ja0271781

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

Electronic structure, local magnetism, and spin-orbit effects of Ir(IV)-, Ir(V)-, and Ir(VI)-based compounds
journal, June 2015


Design and Crystal Growth of Magnetic Double Perovskite Iridates: Ln 2 MIrO 6 ( Ln = La, Pr, Nd, Sm-Gd; M = Mg, Ni)
journal, April 2016

  • Ferreira, Timothy; Morrison, Gregory; Yeon, Jeongho
  • Crystal Growth & Design, Vol. 16, Issue 5
  • DOI: 10.1021/acs.cgd.6b00121

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

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