Synthesis, Characterization, and Magnetic Properties of Uranium-Containing 2H-Perovskite-Related Sulfides: Ba3MUS6 (M = Mn, Fe, Co, Ni) and Ba3Co0.858(5)Mg0.142(5)US6

Breton, Logan S.; Morrison, Gregory; zur Loye, Hans-Conrad

doi:10.1021/acs.inorgchem.3c02749

Cited by 2 publications

(1 citation statement)

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“…Transition and post-transition metal (M) sulfides form a huge family of materials which have been investigated mainly for their optical, ionic, electrical, and thermal properties. These properties are particularly crucial for various applications including optoelectronic devices, , catalysis and photocatalysis, magnetism, and energy-related applications, such as solid-state batteries, − magnetocalorics, solar cells, , or thermoelectricity. − However, a significant aspect of research on thermoelectrics is to find a material able to exhibit simultaneously high electrical conductivity and low thermal conductivity . The antagonist character of these two properties means that they cannot be easily optimized within the same metal–sulfur (M–S) lattice, leading to a compromise between the two effects.…”

Section: Introductionmentioning

confidence: 99%

Is the Presence of Sn²⁺ a Crucial Factor for the Generation of Low Thermal Conductivity in Tin-Based Sulfides?

Guiot,

Prestipino,

Guilmeau

et al. 2024

Inorg. Chem.

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Comprehending the relationship between crystal structures and transport properties is crucial to develop materials with improved electrical and thermal properties for thermoelectric applications. In this article, we report on the complex crystal structure and physical properties of Cr 2 Sn 3 S 7 , a n-type magnetic semiconductor with a low energy band gap and low thermal conductivity. Importantly, we demonstrate that the high level of structural complexity is related to the coexistence of two sublattices: a host lattice, [Cr 4 Sn 2 S 11 ] 2− , characterized by a mixed Sn 4+ /Cr 3+ occupancy of its cationic sites, and a guest lattice characterized by [Sn 4 S 3 ] 2+ chains, containing Sn 2+ cations only, closely related to the ones encountered in the orthorhombic SnS compound. By combining experiments including X-ray diffraction with ab initio calculations of electrons and phonons, we succeeded to elucidate the origin of the low thermal conductivity in Cr 2 Sn 3 S 7. We demonstrate that the low dimensionality of the [Sn 4 S 3 ] 2+ chains, which generates weak Sn•••S interactions with the 3D host lattice, is induced by the lone pair stereochemical activity of Sn 2+ . This lattice softening favors strong anisotropic vibrations at low frequencies, highlighting the primordial role played by Sn 2+ cations in both crystal structure dimensionality and low thermal conductivity in tin-based sulfides. 2 =, where S, σ, κ, and T represent the Seebeck coefficient or thermopower, electrical conductivity, total thermal conductivity, and operating absolute temperature, respectively). This anisotropy in the

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Section: Introductionmentioning

confidence: 99%

Is the Presence of Sn²⁺ a Crucial Factor for the Generation of Low Thermal Conductivity in Tin-Based Sulfides?

Guiot,

Prestipino,

Guilmeau

et al. 2024

Inorg. Chem.

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Rare Bird: U⁺⁵ in Uranium Chalcogenides

Berseneva,

Klepov,

Kashem

et al. 2024

Chem. Mater.

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Chalcogen environments tend to stabilize low oxidation states, thus making the +5 oxidation state in uranium chalcogenides extremely rare. Having one unpaired electron, the magnetism of U+5, 5f1, is of significant interest; however, it is underexplored due to a scarcity of examples. Three related all-U+5 chalcogenides, Na2Cu5US6, Na3Cu4US6, and Na3Cu4USe6, were obtained as single crystals via the flux-assisted boron chalcogen mixture method as part of a broader investigation of the Na–Cu–U–Q (Q = S and Se) systems. To test the formation of the Se-analog of Na2Cu5US6, we performed in situ high-temperature powder X-ray diffraction using sealed capillaries; this approach demonstrated the formation and presence of only Na3Cu4USe6 and not “Na2Cu5USe6” in the reaction mixture. In addition to assigning oxidation states using charge balance and the sample composition, oxidation states of copper, +1, and uranium, +5, in Na2Cu5US6 were also determined via X-ray absorption near edge spectroscopy. Magnetic properties were investigated on both bulk powder samples of Na2Cu5US6 and Na3Cu4UQ 6 (Q = S and Se) and millimeter-size single crystals of Na2Cu5US6, where magnetic susceptibility and magnetization vs field measurements revealed antiferromagnetic behavior of Na2Cu5US6 and Na3Cu4UQ 6 (Q = S and Se) with a T N of 4.7, 3.4, and 5.9 K, respectively. Finally, a broad discussion of the effective magnetic moment of U+5, which is significantly smaller, 1.06 μB in Na2Cu5US6 and 1.08 μB in Na3Cu4USe6, than predicted by spin-only (1.73 μB) and total angular momentum (2.54 μB) models. The fact that only about 20 compositions of such materials are currently known, highlights the need to explore additional compositions containing uranium in rare oxidation states before it will be possible to understand the magnetic properties of such materials more fully.

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Synthesis, Characterization, and Magnetic Properties of Uranium-Containing 2H-Perovskite-Related Sulfides: Ba₃MUS₆ (M = Mn, Fe, Co, Ni) and Ba₃Co_0.858(5)Mg_0.142(5)US₆

Cited by 2 publications

References 45 publications

Is the Presence of Sn²⁺ a Crucial Factor for the Generation of Low Thermal Conductivity in Tin-Based Sulfides?

Is the Presence of Sn²⁺ a Crucial Factor for the Generation of Low Thermal Conductivity in Tin-Based Sulfides?

Rare Bird: U⁺⁵ in Uranium Chalcogenides

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Synthesis, Characterization, and Magnetic Properties of Uranium-Containing 2H-Perovskite-Related Sulfides: Ba3MUS6 (M = Mn, Fe, Co, Ni) and Ba3Co0.858(5)Mg0.142(5)US6

Cited by 2 publications

References 45 publications

Is the Presence of Sn2+ a Crucial Factor for the Generation of Low Thermal Conductivity in Tin-Based Sulfides?

Is the Presence of Sn2+ a Crucial Factor for the Generation of Low Thermal Conductivity in Tin-Based Sulfides?

Rare Bird: U+5 in Uranium Chalcogenides

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Synthesis, Characterization, and Magnetic Properties of Uranium-Containing 2H-Perovskite-Related Sulfides: Ba₃MUS₆ (M = Mn, Fe, Co, Ni) and Ba₃Co_0.858(5)Mg_0.142(5)US₆

Is the Presence of Sn²⁺ a Crucial Factor for the Generation of Low Thermal Conductivity in Tin-Based Sulfides?

Is the Presence of Sn²⁺ a Crucial Factor for the Generation of Low Thermal Conductivity in Tin-Based Sulfides?

Rare Bird: U⁺⁵ in Uranium Chalcogenides