Structures and Magnetic Properties of K₂Pd₄U₆S₁₇, K₂Pt₄U₆S₁₇, Rb₂Pt₄U₆S₁₇, and Cs₂Pt₄U₆S₁₇ Synthesized Using the Boron–Chalcogen Mixture Method

Abstract

A series of A2M4U6S17 (A = alkali metal; M = Pd, Pt) compounds, specifically K2Pd4U6S17, K2Pt4U6S17, Rb2Pt4U6S17, and Cs2Pt4U6S17, were synthesized using the combined boron–chalcogen mixture and molten flux crystal growth methods. The formation of rubidium- and cesium-containing analogues resulted from a in situ alkali polysulfide flux formed from alkali carbonates. The successful synthesis of single crystals of the title compounds allowed for their structural characterization by single-crystal X-ray diffraction. The structure determination revealed disorder of the alkali cations in Rb2Pt4U6S17 and Cs2Pt4U6S17, while the potassium cations in K2Pd4U6S17 and K2Pt4U6S17 were fully ordered. Magnetic measurements were performed on samples of K2Pt4U6S17, Rb2Pt4U6S17, and Cs2Pt4U6S17 that contained small amounts of paramagnetic β-US2 and diamagnetic PtS. Antiferromagnetic order was observed at T N = 9.1 K for K2Pt4U6S17. No long-range magnetic order was observed for Rb2Pt4U6S17 and Cs2Pt4U6S17. Uranium moments of 2.5, 2.6, and 2.6 μB were measured for K2Pt4U6S17, Rb2Pt4U6S17, and Cs2Pt4U6S17, respectively.

Advances in Chalcogenide Crystal Growth: Flux and Solution Syntheses, and Approaches for Postsynthetic Modifications

“…79 They obtained novel lanthanide and actinide chalcogenides by coupling the BCM method with flux crystal growth (Figure 7). 29,79,86,87 As a continuous study, the zur Loye group evaluated the BCM method for flux crystal growth of transuranium chalcogenides and synthesized single crystals of NaCuNpS 3 . 29 For the first time, a transuranium chalcogenide was obtained using NpO 2 instead of Np metal as a starting reagent, which creates a convenient route for synthesizing novel transuranium chalcogenide materials.…”

Crystal Growth of Quaternary AkRE2Si2S8 (Ak = Ca and Sr; RE = La–Tb) Thiosilicates Using Flux-Assisted Boron Chalcogen Mixture Method: Exploring X-ray Scintillation, Luminescence, and Magnetic Properties

“…The zur Loye group has addressed this issue by employing the boron chalcogen mixture (BCM) method, which provides a straightforward route for synthesizing mixed metal chalcogenides starting from metal oxide precursors. Many lanthanides and actinides containing chalcogenides, including thiophosphates and thiosilicates, were previously reported synthesized using the BCM synthesis route. − Despite the existence of several reported series of thiosilicates, there remains significant room for the exploration of additional structural families and compositions, which is made possible by the thiosilicates’ extensive structural flexibility. − Recently, the zur Loye group reported on two series of quaternary thiosilicates (RE 3 Mg 0.5 SiS 7 and RE 3 TM 0.5 SiS 7 ), , a class of chalcometallates synthesized via the BCM method. During the synthesis of the RE 3 Mg 0.5 SiS 7 series, we observed the presence of a trace secondary phase, identified as CaCe 2 Si 2 S 8 , where calcium originated from the flux used for crystal growth.…”

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

“…Mesbah et al have discovered many 2H-perovskite related uranium sulfides and selenides and reported on their synthesis and characterization. The magnetic behavior of the reported compounds, however, could not be determined due to side products and UOQ (Q = S, Se) impurities that could not be separated from the reaction products, which complicates magnetic measurements. , Our group recently developed the boron–chalcogen mixture (BCM) method for actinides, and has used this method to obtain a multitude of actinide containing chalcogenides. − The success of this method prompted us to expand the method toward the system of 2H-perovskite-related uranium sulfides to resynthesize some known compounds, to explore their magnetic behaviors, as well as to synthesize new compositions to add to the limited number of existing compounds. Herein, we report on the synthesis and magnetic behavior of two known 2H-perovskite-related uranium chalcogenides with the formula Ba 3 MUS 6 (M = Mn, Fe), as well as on the synthesis and characterization of three new additions to the family, Ba 3 NiUS 6 , Ba 3 CoUS 6 , and Ba 3 Co 0.858(5) Mg 0.142(5) US 6 , including the magnetic behavior of Ba 3 NiUS 6 .…”