Structural, optical, and magnetic properties of Na{sub 8}Eu{sub 2}(Si{sub 2}S{sub 6}){sub 2} and Na{sub 8}Eu{sub 2}(Ge{sub 2}S{sub 6}){sub 2}: Europium(II) quaternary chalcogenides that contain an ethane-like (Si{sub 2}S{sub 6}){sup 6−} or (Ge{sub 2}S{sub 6}){sup 6−} moiety
- Department of Chemistry, Missouri University of Science and Technology, Rolla, MO 65409-0010 (United States)
- Department of Physics, Astronomy, and Materials Science and the Center for Applied Science and Engineering, Missouri State University, Springfield, MO 65897 (United States)
- Department of Chemistry, Colorado State University, Fort Collins, CO 80523 (United States)
Two isostructural europium(II) quaternary chalcogenides, Na{sub 8}Eu{sub 2}(Si{sub 2}S{sub 6}){sub 2}, 1, and Na{sub 8}Eu{sub 2}(Ge{sub 2}S{sub 6}){sub 2}, 2, containing an ethane-like (Si{sub 2}S{sub 6}){sup 6−} or (Ge{sub 2}S{sub 6}){sup 6−} moiety have been synthesized by employing the polychalcogenide molten flux method. Single-crystal X-ray diffraction reveals that both compounds crystallize in the C2/m space group, and their structures contain layers of ([Na{sub 2}Eu{sub 2}(Si{sub 2}S{sub 6}){sub 2}]{sup 6−}){sub ∞} or ([Na{sub 2}Eu{sub 2}(Ge{sub 2}S{sub 6}){sub 2}]{sup 6−}){sub ∞} anions held together by six interlayer sodium cations to yield (Na{sub 6}[Na{sub 2}Eu{sub 2}(Si{sub 2}S{sub 6}){sub 2}]){sub ∞} and (Na{sub 6}[Na{sub 2}Eu{sub 2}(Ge{sub 2}S{sub 6}){sub 2}]){sub ∞}. Compound 2 is a semiconductor with an optical band gap of 2.15(2) eV. The temperature dependence of the magnetic susceptibility indicates that compounds 1 and 2 are paramagnetic with μ{sub eff}=7.794(1) μ{sub B} per Eu and g=1.964(1) for 1 and μ{sub eff}=8.016(1) μ{sub B} per Eu and g=2.020(1) for 2, moments that are in good agreement with the europium(II) spin-only moment of 7.94 μ{sub B}. The europium-151 Mössbauer isomer shift of 2 confirms the presence of europium(II) cations with an electronic configuration between [Xe]4f{sup 6.81} and 4f{sup 7}6s{sup 0.32}. - Graphical abstract: TOC figure caption: structure of Na{sub 8}Eu{sub 2}(Si{sub 2}S{sub 6}){sub 2} viewed along the a-axis showing the filling of A–B and B–A types of anion layers with two different types of cations. - Highlights: • Synthesis of quaternary europium chalcogenides containing ethane-like dimer. • Structural characterization employing single-crystal X-ray diffraction. • Mössbauer spectroscopy and magnetic measurements confirm presence of Eu(II)
- OSTI ID:
- 22475638
- Journal Information:
- Journal of Solid State Chemistry, Vol. 226; Other Information: Copyright (c) 2015 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ANIONS
CATIONS
DIMERS
ELECTRONIC STRUCTURE
ETHANE
EUROPIUM COMPOUNDS
GERMANIUM SULFIDES
ISOMER SHIFT
LAYERS
MAGNETIC SUSCEPTIBILITY
MONOCLINIC LATTICES
MONOCRYSTALS
PARAMAGNETISM
SEMICONDUCTOR MATERIALS
SILICON SULFIDES
SODIUM COMPOUNDS
SYNTHESIS
TEMPERATURE DEPENDENCE
X-RAY DIFFRACTION