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• W3000739265 abstract "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, Tl2-xBixOs2O7-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 (Fd3m), 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." @default.
• W3000739265 created "2020-01-23" @default.
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• W3000739265 date "2020-01-07" @default.
• W3000739265 modified "2023-09-23" @default.
• W3000739265 title "Os⁴⁺ Instability in the Pyrochlore Structure: Tl_2–<i>x</i>Bi_<i>x</i>Os₂O_7–<i>y</i>" @default.
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• W3000739265 doi "https://doi.org/10.1021/acs.inorgchem.9b02939" @default.
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