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Title: The Crystal Structure and Magnetic Behavior of Quinary Osmate and Ruthenate Double Perovskites La ABB'O 6 (A = Ca, Sr; B = Co, Ni; B' = Ru, Os)

Abstract

In this work, six LaABB'O6 (A = Ca, Sr; B = Co, Ni; B' = Ru, Os) double perovskites were synthesized, several for the first time, and their crystal structures and magnetic behavior were characterized with neutron powder diffraction and direct-current and alternating-current magnetometry. All six compounds crystallize with P21/n space group symmetry, resulting from aac+ octahedral tilting and complete rock salt ordering of transition-metal ions. Despite the electronic configurations of the transition-metal ions, either d8–d3 or d7–d3, not one of the six compounds shows ferromagnetism as predicted by the Goodenough–Kanamori rules. LaSrNiOsO6, LaSrNiRuO6, and LaCaNiRuO6 display long-range antiferromagnetic order, while LaCaNiOsO6, LaCaCoOsO6, and LaSrCoOsO6 exhibit spin-glass behavior. These compounds are compared to the previously studied LaCaCoRuO6 and LaSrCoRuO6, both of which order antiferromagnetically. Lastly, the observed variations in magnetic properties can be attributed largely to the response of competing superexchange pathways due to changes in B–O–B' bond angles, differences in the radial extent of the 4d (B' = Ru) and 5d (B' = Os) orbitals, and filling of the t2g orbitals of the 3d ion.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. The Ohio State Univ., Columbus, OH (United States). Department of Chemistry and Biochemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Univ. of Tennessee, Knoxville, TN (United States). Department of Materials Science and Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1427710
Grant/Contract Number:  
AC05-00OR22725
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

Morrow, Ryan, McGuire, Michael A., Yan, Jiaqiang, and Woodward, Patrick M. The Crystal Structure and Magnetic Behavior of Quinary Osmate and Ruthenate Double Perovskites La ABB'O 6 (A = Ca, Sr; B = Co, Ni; B' = Ru, Os). United States: N. p., 2018. Web. https://doi.org/10.1021/acs.inorgchem.7b02282.
Morrow, Ryan, McGuire, Michael A., Yan, Jiaqiang, & Woodward, Patrick M. The Crystal Structure and Magnetic Behavior of Quinary Osmate and Ruthenate Double Perovskites La ABB'O 6 (A = Ca, Sr; B = Co, Ni; B' = Ru, Os). United States. https://doi.org/10.1021/acs.inorgchem.7b02282
Morrow, Ryan, McGuire, Michael A., Yan, Jiaqiang, and Woodward, Patrick M. Fri . "The Crystal Structure and Magnetic Behavior of Quinary Osmate and Ruthenate Double Perovskites La ABB'O 6 (A = Ca, Sr; B = Co, Ni; B' = Ru, Os)". United States. https://doi.org/10.1021/acs.inorgchem.7b02282. https://www.osti.gov/servlets/purl/1427710.
@article{osti_1427710,
title = {The Crystal Structure and Magnetic Behavior of Quinary Osmate and Ruthenate Double Perovskites La ABB'O 6 (A = Ca, Sr; B = Co, Ni; B' = Ru, Os)},
author = {Morrow, Ryan and McGuire, Michael A. and Yan, Jiaqiang and Woodward, Patrick M.},
abstractNote = {In this work, six LaABB'O6 (A = Ca, Sr; B = Co, Ni; B' = Ru, Os) double perovskites were synthesized, several for the first time, and their crystal structures and magnetic behavior were characterized with neutron powder diffraction and direct-current and alternating-current magnetometry. All six compounds crystallize with P21/n space group symmetry, resulting from a–a–c+ octahedral tilting and complete rock salt ordering of transition-metal ions. Despite the electronic configurations of the transition-metal ions, either d8–d3 or d7–d3, not one of the six compounds shows ferromagnetism as predicted by the Goodenough–Kanamori rules. LaSrNiOsO6, LaSrNiRuO6, and LaCaNiRuO6 display long-range antiferromagnetic order, while LaCaNiOsO6, LaCaCoOsO6, and LaSrCoOsO6 exhibit spin-glass behavior. These compounds are compared to the previously studied LaCaCoRuO6 and LaSrCoRuO6, both of which order antiferromagnetically. Lastly, the observed variations in magnetic properties can be attributed largely to the response of competing superexchange pathways due to changes in B–O–B' bond angles, differences in the radial extent of the 4d (B' = Ru) and 5d (B' = Os) orbitals, and filling of the t2g orbitals of the 3d ion.},
doi = {10.1021/acs.inorgchem.7b02282},
journal = {Inorganic Chemistry},
number = 6,
volume = 57,
place = {United States},
year = {2018},
month = {2}
}

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Figures / Tables:

Figure 1 Figure 1: The upper half depicts AFM-I and AFM-II structures commonly found on the double perovskite pseudo FCC when only either B or B’ is a magnetic transition metal cation. For AFM-I, any given magnetic cation has 8 NN AFM pairs and 4 FM NN pairs while having 6 FMmore » NNN pairs. For AFM-II, it has 6 NN AFM pairs and 6 FM NN pairs while having 6 of 6 NNN AFM pairs. The lower half depicts ferro- and ferrimagnetism which results from heteroatomic coupling. Compound examples which manifest each type of magnetic behavior are given.« less

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    Works referencing / citing this record:

    Long- and short-range magnetism in the frustrated double perovskite B a 2 MnW O 6
    journal, January 2020