Os4+ Instability in the Pyrochlore Structure: Tl2–xBixOs2O7–y

Converse, Elizabeth Sobalvarro; Li, Jun; Haskel, Daniel; LaBarre, Patrick G.; Ramirez, Arthur P.; Subramanian, M. A.

doi:10.1021/acs.inorgchem.9b02939

Title: Os⁴⁺ Instability in the Pyrochlore Structure: Tl_2–xBi_xOs₂O_7–y

Journal Article · 06 January 2020 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.9b02939 · OSTI ID:1606534

Converse, Elizabeth Sobalvarro ^[1]; Li, Jun ^[1]; Haskel, Daniel ^[2]; LaBarre, Patrick G. ^[3]; Ramirez, Arthur P. ^[3];

^[1]

Oregon State Univ., Corvallis, OR (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Univ. of California, Santa Cruz, CA (United States)

Osmium-containing oxides are rare due to the difficulty in stabilizing complex structures with a fixed stoichiometry and metastability of the phases. Bismuth-substituted thallium osmate pyrochlore samples, Tl_2–xBi_xOs₂O_7–y, were synthesized using solid-state reactions where the solubility limit was found to be approximately x = 1.4. Members of this solid solution were characterized by their structural, electronic, magnetic, and thermal properties to understand the influence of Bi3+ substitution on the ground state. The Os-containing pyrochlores crystallize in the ideal cubic pyrochlore structure (Fd (3) over barm), and the lattice parameter a was found to slightly increase as a function of Bi content. A possible interplay between structure and cation valence states was explored using both neutron powder diffraction and X-ray absorption spectroscopy, suggesting that a combination of Os⁴⁺/Os⁵⁺ and Tl¹⁺/Tl³⁺ mixed valency throughout the solid solution allows for the stabilization of the pyrochlore structure. The system is metallic for the entire solid solution and predominantly exhibits temperature-independent paramagnetism. Specific heat measurements show an enhanced Sommerfeld coefficient, a possible flat-band signature. This system gave insight into the bonding preferences of Os, indicating a dependence on high oxidation states and mixed valence for the stability of complex structures.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1606534

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 2 Vol. 59; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (21)

Structural and Electronic Factors Governing the Metallic and Nonmetallic Properties of the PyrochloresA2Ru2O7−y Lee, K. -S.; Seo, D. -K.; Whangbo, M. -H. Journal of Solid State Chemistry, Vol. 131, Issue 2 https://doi.org/10.1006/jssc.1997.7497	journal	July 1997
Platinum metal pyrochlores of the type Tl2M2O7 Sleight, A. W.; Gillson, J. L. Materials Research Bulletin, Vol. 6, Issue 8 https://doi.org/10.1016/0025-5408(71)90114-0	journal	August 1971
Ln2Os2O7 — A new family of pyrochlores Shaplygin, I. S.; Lazarev, V. B. Materials Research Bulletin, Vol. 8, Issue 7 https://doi.org/10.1016/0025-5408(73)90181-5	journal	July 1973
New ternary oxides of Re, Os, Ir and Pt with cubic crystal structures Sleight, Arthur W. Materials Research Bulletin, Vol. 9, Issue 9 https://doi.org/10.1016/0025-5408(74)90035-X	journal	September 1974
Semiconductor-metal transition in novel Cd2Os2O7 Sleight, A. W.; Gillson, J. L.; Weiher, J. F. Solid State Communications, Vol. 14, Issue 4 https://doi.org/10.1016/0038-1098(74)90917-X	journal	February 1974
Universal relationship of the resistivity and specific heat in heavy-Fermion compounds Kadowaki, K.; Woods, S. B. Solid State Communications, Vol. 58, Issue 8 https://doi.org/10.1016/0038-1098(86)90785-4	journal	May 1986
Thermal stability of osmium mixed oxides I. CaOsO3 decomposition products: A new orthorhombic phase Ca2Os2O7 Shaplygin, I. S.; Lazarev, V. B. Thermochimica Acta, Vol. 20, Issue 3 https://doi.org/10.1016/0040-6031(77)85092-2	journal	September 1977
Thermal stability of osmium mixed oxides. II. CaOsO3 decomposition products: condition formation of defect pyrochlores Ca2Os2O7 Shaplygin, I. S.; Lazarev, V. B. Thermochimica Acta, Vol. 32, Issue 1-2 https://doi.org/10.1016/0040-6031(79)85090-X	journal	September 1979
Oxide pyrochlores — A review Subramanian, M. A.; Aravamudan, G.; Subba Rao, G. V. Progress in Solid State Chemistry, Vol. 15, Issue 2 https://doi.org/10.1016/0079-6786(83)90001-8	journal	January 1983
Transport, thermal and magnetic properties of Bi3Os3O11 and Bi3Ru3O11 Fujita, T. Physica B: Condensed Matter, Vol. 329-333 https://doi.org/10.1016/S0921-4526(02)02483-3	journal	May 2003
Accurate heat capacity measurements on powdered samples using a Quantum Design physical property measurement system Shi, Quan; Snow, Claine L.; Boerio-Goates, Juliana The Journal of Chemical Thermodynamics, Vol. 42, Issue 9 https://doi.org/10.1016/j.jct.2010.04.008	journal	September 2010
Bi _{2– x} Ca _x Ir ₂ O _{6+ y} Pyrochlore Phases: Structure and Properties with Varied Ir Oxidation State from 3.9+ to 4.3+ Giampaoli, Gabriella; Li, Jun; Ramirez, Arthur P. Inorganic Chemistry, Vol. 56, Issue 8 https://doi.org/10.1021/acs.inorgchem.7b00345	journal	April 2017
Local Moment Instability of Os in Honeycomb Li2.15Os0.85O3 Wallace, M. K.; LaBarre, P. G.; Li, Jun Scientific Reports, Vol. 8, Issue 1 https://doi.org/10.1038/s41598-018-25028-0	journal	April 2018
Syntheses, structures and properties of some osmates(iv,v) adopting the pyrochlore and weberite structures Reading, J.; Knee, C. S.; Weller, M. T. Journal of Materials Chemistry, Vol. 12, Issue 8 https://doi.org/10.1039/b201410f	journal	June 2002
High-pressure synthesis, crystal structure, and magnetic properties of KSbO ₃ -type 5 d oxides K _0.84 OsO ₃ and Bi _2.93 Os ₃ O ₁₁ Yuan, Yahua; Feng, Hai L.; Shi, Youguo Science and Technology of Advanced Materials, Vol. 15, Issue 6 https://doi.org/10.1088/1468-6996/15/6/064901	journal	December 2014
Topological insulators and metal-insulator transition in the pyrochlore iridates Yang, Bohm-Jung; Kim, Yong Baek Physical Review B, Vol. 82, Issue 8 https://doi.org/10.1103/PhysRevB.82.085111	journal	August 2010
Fragility of ferromagnetic double exchange interactions and pressure tuning of magnetism in 3 d − 5 d double perovskite Sr 2 FeOsO 6 Veiga, L. S. I.; Fabbris, G.; van Veenendaal, M. Physical Review B, Vol. 91, Issue 23 https://doi.org/10.1103/PhysRevB.91.235135	journal	June 2015
Superconductivity at 1 K in Cd 2 Re 2 O 7 Hanawa, M.; Muraoka, Y.; Tayama, T. Physical Review Letters, Vol. 87, Issue 18 https://doi.org/10.1103/PhysRevLett.87.187001	journal	October 2001
EXPGUI , a graphical user interface for GSAS Toby, Brian H. Journal of Applied Crystallography, Vol. 34, Issue 2 https://doi.org/10.1107/S0021889801002242	journal	April 2001
The automatic searching for chemical bonds in inorganic crystal structures Altermatt, D.; Brown, I. D. Acta Crystallographica Section B Structural Science, Vol. 41, Issue 4 https://doi.org/10.1107/S0108768185002051	journal	August 1985
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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CSD 1957325: Experimental Crystal Structure Determination Sobalvarro, Converse, Elizabeth; Jun, Li,; Daniel, Haskel, https://doi.org/10.25505/fiz.icsd.cc23prj3 The current record is supplemented by this dataset	dataset	January 2020
CSD 1957326: Experimental Crystal Structure Determination Sobalvarro, Converse, Elizabeth; Jun, Li,; Daniel, Haskel, https://doi.org/10.25505/fiz.icsd.cc23prk4 The current record is supplemented by this dataset	dataset	January 2020
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Title: Os4+ Instability in the Pyrochlore Structure: Tl2–xBixOs2O7–y

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References (21)

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Title: Os⁴⁺ Instability in the Pyrochlore Structure: Tl_2–xBi_xOs₂O_7–y