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Structure modification on quaternary rare earth thiophosphates: NaYbP2S6, NaSmP2S6, and KSmP2S7

Title
Structure modification on quaternary rare earth thiophosphates: NaYbP2S6, NaSmP2S6, and KSmP2S7
Authors
Goh E.-Y.Kim E.-J.Kim S.-J.
Ewha Authors
김성진
SCOPUS Author ID
김성진scopus
Issue Date
2001
Journal Title
Journal of Solid State Chemistry
ISSN
0022-4596JCR Link
Citation
vol. 160, no. 1, pp. 195 - 204
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Three rare earth quaternary compounds, NaYbP2S6, NaSmP2S6, and KSmP2S7, are synthesized using alkali metal halide or polychalcogenides flux. NaYbP2S6 was prepared from the stoichiometric reaction of Yb/S/P/NaCl flux at 700°C, and NaSmP2S6 and KSmP2S7 were prepared from Sm/S/P/Na2S (K2Sx) flux at 750°C. The structures were determined by the single-crystal X-ray diffraction technique. The air-sensitive dark-red crystals of NaYbP2S6 crystallize in the triclinic space group P-1 with a=6.8241(10) Å, b=7.0371(10) Å, c=9.107(2) Å, α=87.17(2)°, β=87.62(2)°, γ=88.30(2)°, and Z=2. The yellow plate crystals of NaSmP2S6 crystallize in the monoclinic space group P21/a with a=11.0717(10) Å, b=7.2999(1) Å, c=11.579(3) Å, β=111.30(2)°, and Z=4. The pale yellow plate crystals of KSmP2S7 crystallize in the monoclinic space group P21/a with a=8.981(2) Å, b=12.254(2) Å, c=9.609(1) Å, β=90.27(2)°, and Z=4. NaYbP2S6 and NaSmP2S6 are derivatives of the MIMIIIP2S6 family. NaYbP2S6 has a flat mono layered structure, and there are weak interactions between neighboring layers. In NaSmP2S6, two MPS3-type layers are condensed together. The ordering features of sodium and rare earth metal cations in two-dimensional layers are different: Na and Yb atoms are arranged in pairing fashion in NaYbP2S6, while Na and Sm atoms are arranged in a triangular pattern in NaSmP2S6. The structure of KSmP2S7 is similar to that of ABiP2S7 (A=K, Rb), where corrugated layers are formed from Sm3+ and [P2S7]4- units. The optically measured band gaps of NaYbP2S6 and NaSmP2S6 are 1.85 eV and 2.54 eV, respectively. © 2001 Academic Press.
DOI
10.1006/jssc.2001.9222
Appears in Collections:
자연과학대학 > 화학·나노과학전공 > Journal papers
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