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  Structure and properties of α-NaFeO2-type ternary sodium iridates

Baroudi, K., Yim, C., Wu, H., Huang, Q., Roudebush, J. H., Vavilova, E., et al. (2014). Structure and properties of α-NaFeO2-type ternary sodium iridates. Journal of Solid State Chemistry, 210(1), 195-205. doi:10.1016/j.jssc.2013.11.017.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0017-B518-4 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002D-71CA-7
Genre: Journal Article

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Baroudi, Kristen1, Author
Yim, Cindi1, Author
Wu, Hui1, Author
Huang, Qingzhen1, Author
Roudebush, John H.1, Author
Vavilova, Eugenia1, Author
Grafe, Hans-Joachim1, Author
Kataev, Vladislav1, Author
Buechner, Bernd1, Author
Ji, Huiwen1, Author
Kuo, Changyang2, Author              
Hu, Zhiwei3, Author              
Pi, Tu-Wen4, Author              
Pao, Chiwen1, Author
Lee, Jyhfu1, Author
Mikhailova, Daria5, Author              
Tjeng, Liu Hao6, Author              
Cava, R. J.1, Author
Affiliations:
1external, ou_persistent22              
2Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863445              
3Zhiwei Hu, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863461              
4Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863404              
5Daria Mikhailova, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863448              
6Liu Hao Tjeng, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863452              

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 Abstract: The synthesis, structure, and elementary magnetic and electronic properties are reported for layered compounds of the type Na3-xMIr2O6 and Na3-xM2IrO6, where M is a transition metal from the 3d series (M=Zn, Cu, Ni, Co, Fe and Mn). The rhombohedral structures, in space group R-3m, were determined by refinement of neutron and synchrotron powder diffraction data. No clear evidence for long range 2:1 or 1:2 honeycomb-like M/Ir ordering was found in the neutron powder diffraction patterns except in the case of M=Zn, and thus in general the compounds are best designated as sodium deficient alpha-NaFeO2-type Phases with formulas Na1-xM1/3Ir2/3O2 or Na1-xM2/3Ir1/3O2. Synchrotron powder diffraction patterns indicate that several of the compounds likely have honeycomb in-plane metal-iridium ordering with disordered stacking of the layers. All the compounds are sodium deficient under our synthetic conditions and are black and insulating. Weiss constants derived from magnetic susceptibility measurements indicate that Na0.62Mn0.61Ir0.39O2, Na0.80Fe2/3Ir1/3O2, Na0.92Ni1/3Ir2/3O2, Na0.86Cu1/3Ir2/3O2, and Na0.89Zn1/3Ir2/3O2 display dominant antiferromagnetic interactions. For Na0.90Co1/3Ir2/3O2 the dominant magnetic interactions at low temperature are ferromagnetic while at high temperatures they are antiferromagnetic; there is also a change in the effective moment. Low temperature specific heat measurements (to 2 K) on Na0.32Ni1/3Ir2/3O2 indicate the presence of a broad magnetic ordering transition. X-ray absorption spectroscopy shows that iridium is at or close to the 4+ oxidation state in all compounds. Na-23 nuclear magnetic resonance measurements comparing Na2IrO3 to Na0.92Ni1/3Ir2/3O2 and Na0.89Zn1/3Ir2/3O2 provide strong indications that the electron spins are short-range ordered in the latter two materials. Na0.62Mn0.61Ir0.39O2, Na0.80Fe2/3Ir1/3O2, Na0.90Co1/3Ir2/3O2, Na0.92Ni1/3Ir2/3O2, Na0.86Cu1/3Ir2/3O2 and Na0.89Zn1/3Ir2/3O2 are spin glasses. (CSD-numbers: Na0.62Mn0,61Ir0.39O2: 426657, Na0.80Fe2/3Ir1/3O2: 426659, Na0.90Co1/3Ir2/3O2: 426658, Na0.92Ni1/3Ir2/3O2: 426656, Na0.86Cu1/3Ir2/3O2: 426655, and Na2.8ZnIr2O6: 426660.) (C) 2013 Elsevier Inc. All rights reserved.

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 Dates: 2014-02-01
 Publication Status: Published in print
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Title: Journal of Solid State Chemistry
Source Genre: Journal
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Publ. Info: Orlando, Fla. : Academic Press
Pages: - Volume / Issue: 210 (1) Sequence Number: - Start / End Page: 195 - 205 Identifier: ISSN: 0022-4596
CoNE: /journals/resource/954922646045