The first examples of alkali metal/Cu/Ce/chalcogenides: The layered heterometallic compounds KCuCe2S6 and K2Cu2CeS4

Anthony C. Sutorik, Joyce Albritton-Thomas, Carl R. Kannewurf, Mercouri G Kanatzidis

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Abstract

From the reaction of the metallic elements in molten alkali metal/polychalcogenide fluxes, we have synthesized KCuCe2S6 (I) and K2Cu2CeS4 (II). Isolated from a 2/0.5/1/8 mixture of K2S/Cu/Ce/S heated at 270 °C for 6 d, I crystallizes in the space group C2/c (no. 15) with a = 6.859(2) Å, b = 21.154(2) Å, c = 6.8599(8) Å, β = 105.41(2)°, and Z = 4. The structure of I features (CuCe2S6)nn- anionic layers composed of [CeS8] bicapped trigonal prisms connected in the ZrSe3 fashion with Cu+ residing in tetrahedral sites within the layers and K+ cations in the interlayer gallery. Diffuse reflectance measurements have shown an approximated band gap of 1.8 eV for I, and magnetic studies exhibit Curie-Weiss paramagnetic behavior at temperatures above 160 K with μeff = 3.08 μB/formula. Isolated from a 4.2/0.5/0.25/8 mixture of the above reagents heated at 260 °C for 5d, II crystallizes in the C2/m space group (no. 12) with a = 14.320(3) Å, b = 3.961(1) Å, c = 7.496(2) Å, β = 109.77(2)°, and Z = 2. Compound II is also a layered structure in which Ce atoms, octahedrally coordinated by S, and Cu, tetrahedrally coordinated by S, form anionic layers related to Mg2SiO4 (olivine) with K+ in the interlayer gallery. From magnetic susceptibility studies, a μeff of 2.38 μB was estimated above 150 K corresponding to the value for a lone Ce3+. The compound's oxidation states are formalized as K2(Cu1+)2(Ce3+)(S2-) 3(S1-). Below 150 K, the material shows non-Curie-Weiss behavior, exhibiting a decreasing μeff. Thermopower studies on II show p-type carriers; however, the conductivity is low and increases with increasing temperature, suggesting a low carrier mobility possibly arising from small polaron formation.

Original languageEnglish
Pages (from-to)7706-7713
Number of pages8
JournalJournal of the American Chemical Society
Volume116
Issue number17
Publication statusPublished - Aug 24 1994

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Alkali Metals
Chalcogenides
Alkali metals
Gene Conversion
Olivine
Temperature
Reflectometers
Carrier mobility
Thermoelectric power
Prisms
Magnetic susceptibility
Cations
Molten materials
Energy gap
Positive ions
Fluxes
Atoms
Oxidation
olivine
forsterite

ASJC Scopus subject areas

  • Chemistry(all)

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The first examples of alkali metal/Cu/Ce/chalcogenides : The layered heterometallic compounds KCuCe2S6 and K2Cu2CeS4. / Sutorik, Anthony C.; Albritton-Thomas, Joyce; Kannewurf, Carl R.; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 116, No. 17, 24.08.1994, p. 7706-7713.

Research output: Contribution to journalArticle

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title = "The first examples of alkali metal/Cu/Ce/chalcogenides: The layered heterometallic compounds KCuCe2S6 and K2Cu2CeS4",
abstract = "From the reaction of the metallic elements in molten alkali metal/polychalcogenide fluxes, we have synthesized KCuCe2S6 (I) and K2Cu2CeS4 (II). Isolated from a 2/0.5/1/8 mixture of K2S/Cu/Ce/S heated at 270 °C for 6 d, I crystallizes in the space group C2/c (no. 15) with a = 6.859(2) {\AA}, b = 21.154(2) {\AA}, c = 6.8599(8) {\AA}, β = 105.41(2)°, and Z = 4. The structure of I features (CuCe2S6)nn- anionic layers composed of [CeS8] bicapped trigonal prisms connected in the ZrSe3 fashion with Cu+ residing in tetrahedral sites within the layers and K+ cations in the interlayer gallery. Diffuse reflectance measurements have shown an approximated band gap of 1.8 eV for I, and magnetic studies exhibit Curie-Weiss paramagnetic behavior at temperatures above 160 K with μeff = 3.08 μB/formula. Isolated from a 4.2/0.5/0.25/8 mixture of the above reagents heated at 260 °C for 5d, II crystallizes in the C2/m space group (no. 12) with a = 14.320(3) {\AA}, b = 3.961(1) {\AA}, c = 7.496(2) {\AA}, β = 109.77(2)°, and Z = 2. Compound II is also a layered structure in which Ce atoms, octahedrally coordinated by S, and Cu, tetrahedrally coordinated by S, form anionic layers related to Mg2SiO4 (olivine) with K+ in the interlayer gallery. From magnetic susceptibility studies, a μeff of 2.38 μB was estimated above 150 K corresponding to the value for a lone Ce3+. The compound's oxidation states are formalized as K2(Cu1+)2(Ce3+)(S2-) 3(S1-). Below 150 K, the material shows non-Curie-Weiss behavior, exhibiting a decreasing μeff. Thermopower studies on II show p-type carriers; however, the conductivity is low and increases with increasing temperature, suggesting a low carrier mobility possibly arising from small polaron formation.",
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T2 - The layered heterometallic compounds KCuCe2S6 and K2Cu2CeS4

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N2 - From the reaction of the metallic elements in molten alkali metal/polychalcogenide fluxes, we have synthesized KCuCe2S6 (I) and K2Cu2CeS4 (II). Isolated from a 2/0.5/1/8 mixture of K2S/Cu/Ce/S heated at 270 °C for 6 d, I crystallizes in the space group C2/c (no. 15) with a = 6.859(2) Å, b = 21.154(2) Å, c = 6.8599(8) Å, β = 105.41(2)°, and Z = 4. The structure of I features (CuCe2S6)nn- anionic layers composed of [CeS8] bicapped trigonal prisms connected in the ZrSe3 fashion with Cu+ residing in tetrahedral sites within the layers and K+ cations in the interlayer gallery. Diffuse reflectance measurements have shown an approximated band gap of 1.8 eV for I, and magnetic studies exhibit Curie-Weiss paramagnetic behavior at temperatures above 160 K with μeff = 3.08 μB/formula. Isolated from a 4.2/0.5/0.25/8 mixture of the above reagents heated at 260 °C for 5d, II crystallizes in the C2/m space group (no. 12) with a = 14.320(3) Å, b = 3.961(1) Å, c = 7.496(2) Å, β = 109.77(2)°, and Z = 2. Compound II is also a layered structure in which Ce atoms, octahedrally coordinated by S, and Cu, tetrahedrally coordinated by S, form anionic layers related to Mg2SiO4 (olivine) with K+ in the interlayer gallery. From magnetic susceptibility studies, a μeff of 2.38 μB was estimated above 150 K corresponding to the value for a lone Ce3+. The compound's oxidation states are formalized as K2(Cu1+)2(Ce3+)(S2-) 3(S1-). Below 150 K, the material shows non-Curie-Weiss behavior, exhibiting a decreasing μeff. Thermopower studies on II show p-type carriers; however, the conductivity is low and increases with increasing temperature, suggesting a low carrier mobility possibly arising from small polaron formation.

AB - From the reaction of the metallic elements in molten alkali metal/polychalcogenide fluxes, we have synthesized KCuCe2S6 (I) and K2Cu2CeS4 (II). Isolated from a 2/0.5/1/8 mixture of K2S/Cu/Ce/S heated at 270 °C for 6 d, I crystallizes in the space group C2/c (no. 15) with a = 6.859(2) Å, b = 21.154(2) Å, c = 6.8599(8) Å, β = 105.41(2)°, and Z = 4. The structure of I features (CuCe2S6)nn- anionic layers composed of [CeS8] bicapped trigonal prisms connected in the ZrSe3 fashion with Cu+ residing in tetrahedral sites within the layers and K+ cations in the interlayer gallery. Diffuse reflectance measurements have shown an approximated band gap of 1.8 eV for I, and magnetic studies exhibit Curie-Weiss paramagnetic behavior at temperatures above 160 K with μeff = 3.08 μB/formula. Isolated from a 4.2/0.5/0.25/8 mixture of the above reagents heated at 260 °C for 5d, II crystallizes in the C2/m space group (no. 12) with a = 14.320(3) Å, b = 3.961(1) Å, c = 7.496(2) Å, β = 109.77(2)°, and Z = 2. Compound II is also a layered structure in which Ce atoms, octahedrally coordinated by S, and Cu, tetrahedrally coordinated by S, form anionic layers related to Mg2SiO4 (olivine) with K+ in the interlayer gallery. From magnetic susceptibility studies, a μeff of 2.38 μB was estimated above 150 K corresponding to the value for a lone Ce3+. The compound's oxidation states are formalized as K2(Cu1+)2(Ce3+)(S2-) 3(S1-). Below 150 K, the material shows non-Curie-Weiss behavior, exhibiting a decreasing μeff. Thermopower studies on II show p-type carriers; however, the conductivity is low and increases with increasing temperature, suggesting a low carrier mobility possibly arising from small polaron formation.

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