Structural Investigation of Six Quinary Sulfides Synthesized via the Flux-Assisted Boron-Chalcogen Mixture (BCM) Method: Eu2+Containing Members of the RE3MTQ7(M and T = Transition or Main Group Metals, Q = Chalcogens) Family
Document Type
Article
Abstract
A series of six quinary rare-earth sulfides Ce1.854+Eu1.152+Na0.30SiS7, Ce1.914+Eu1.092+K0.18SiS7, Ce1.964+Eu1.042+Rb0.08SiS7, Ce1.984+Eu1.022+Cs0.05SiS7, Ce1.974+Eu1.032+Ag0.06SiS7, and Ce1.504+Eu1.502+CuSiS7were obtained in an alkali iodide flux using the boron-chalcogen mixture (BCM) method. Single crystal X-ray diffraction was used to determine the structures of the high quality single crystals that were grown; their elemental compositions were confirmed by energy-dispersive spectroscopy (EDS). The compounds crystallize in the hexagonal crystal system in the noncentrosymmetric space group P63. The crystal structure consists of a three-dimensional network composed of mixed cerium and europium bicapped trigonal prisms, isolated SiS4tetrahedra, and monovalent metals (Na, K, Rb, Cs, Ag, and Cu) located in cavities created by linked Ce/EuS8polyhedra. The structures are charge-balanced when Ce and Eu are in their +4 and +2 oxidation states, respectively. The effective magnetic moment of Ce1.504+Eu1.502+CuSiS7determined from the temperature dependence of the magnetic susceptibility data is consistent with the presence of Ce4+and Eu2+. Clear correlations between the alkali ion site occupancy, the ionic radius of the alkali cations, and the average bond length of Ce4+/Eu2+–S, were established. UV–vis diffuse reflectance data were collected for Ce1.504+Eu1.502+CuSiS7and a band gap of 1.9(1) eV was established.
Digital Object Identifier (DOI)
Publication Info
Published in Inorganic Chemistry, Volume 64, Issue 37, 2025, pages 18799-18808.
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© 2025 American Chemical Society
APA Citation
Tisdale, & zur Loye (2025). Structural Investigation of Six Quinary Sulfides Synthesized Via the Flux-Assisted Boron-Chalcogen Mixture (BCM) Method: Eu2+Containing Members of the R3MTQ7(M and T = Transition or Main Group Metals, Q = Chalcogens) Family. Inorganic Chemistry, 64(37), 18799–18808. https://doi.org/10.1021/acs.inorgchem.5c02443