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

Kashem, Habiba Binte; Tisdale, Hunter B.; zur Loye, Hans-Conrad

doi:10.1021/acs.inorgchem.5c02443

Title: 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

Journal Article · Mon Sep 08 00:00:00 UTC 2025 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.5c02443 · OSTI ID:3015618

Kashem, Habiba Binte ^[1]; Tisdale, Hunter B. ^[1];

^[1]

Univ. of South Carolina, Columbia, SC (United States)

For this work, a series of six quinary rare-earth sulfides Ce⁴⁺_1.85Eu²⁺_1.15Na_0.30SiS₇, Ce⁴⁺_1.91Eu²⁺_1.09K_0.18SiS₇, Ce⁴⁺_1.96Eu²⁺_1.04Rb_0.08SiS₇, Ce⁴⁺_1.98Eu²⁺_1.02Cs_0.05SiS₇, Ce⁴⁺_1.97Eu²⁺_1.03Ag_0.06SiS₇, and Ce⁴⁺_1.50Eu²⁺_1.50CuSiS₇ were 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 SiS4 tetrahedra, and monovalent metals (Na, K, Rb, Cs, Ag, and Cu) located in cavities created by linked Ce/EuS₈ polyhedra. The structures are charge-balanced when Ce and Eu are in their +4 and +2 oxidation states, respectively. The effective magnetic moment of Ce_1.50⁴⁺Eu_1.50²⁺CuSiS₇ determined 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 Ce_1.50⁴⁺Eu_1.50²⁺CuSiS₇ and a band gap of 1.9(1) eV was established.

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Research Organization:: Univ. of South Carolina, Columbia, SC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: SC0018739

OSTI ID:: 3015618

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 37 Vol. 64; ISSN 0020-1669; ISSN 1520-510X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
BCM method
cations
chemical structure
flux crystal growth
metals
rare earth sulfides
silicon

Title: 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

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Title: 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