4성분계 크롬 Thiophosphate 계열 화합물의 합성·구조 및 특성

Author(s)
나주란
Advisor
윤호섭
Department
일반대학원 에너지시스템학부
Publisher
The Graduate School, Ajou University
Publication Year
2010-02
Language
eng
Keyword
Quaternary Chromium ThiophosphatesThiophosphatechalcogenalkali metal flux method
Alternative Abstract
We reported the synthesis of the quaternary alkali metal chromium thiophosphate compounds using reaction of the elements with eutectic alkali metal halide fluxes (KCl/LiCl or RbCl/LiCl or CsCl/LiCl). The crystal structures of the these compounds have been structurally characterized by single crystal X-ray diffraction techniques. The quaternary alkali metal chromium thiophosphate compounds have dark brownish color and a similar shape. First polyhedron-shaped dark brown colored crystal of Cs2CrPS6 crystallizes in the space group P21/n of the monoclinic system with a unit cell parameter ; a = 14.454(5), b = 8.972(3), c = 9.029(3) Å, β = 102.74(3)˚. The structure of contain of molecular cluster, [Cr2P2S12]4-. The molecular cluster of [Cr2P2S12]4- is composed of isolated edge sharing [CrS6] octahedra and [PS4] tetrahedra. This cluster is stabilized through the electrostatic interaction with cesium ions. In conclusion, Cs2CrPS6 compound has zero dimensional character. The ACrPS5(A = Rb, Cs) crystals have dark brown color polyhedra shaped. These compounds crystallized in the monoclinic space group P21/c. The crystal structures of the compounds comprise one dimensional [CrPS5 −] chains separated from one another by alkali metal cations (Rb+, Cs+). The linear chains are built up from the basic repeating unit, [Cr2(PS4)2S2]2-, which is composed of isolated edge sharing [CrS6] octahedra and [PS4] tetrahedra. These repeating units are linked together sharing two μ-S atoms to from the one dimensional [CrPS5 −] chains. The alkali cations spread between chains and there are only van der Waals interactions between them. The classical charge valence can be [A+][Cr4+][P5+][S2-]5(A = Rb, Cs). The ACrP2S7(A = K, Rb, Cs) crystals have needle-plate shaped and dark brown color. These compounds crystallized in the monoclinic space group C2 . The crystal structures of the compounds comprise two dimensional described as [CrP2S7 −] layers separated from one another by alkali metal cations (K+, Rb+, Cs+). The two dimensional structures of ACrP2S7(A = K, Rb, Cs), built from bitetrahadral [P2S7] units sharing edges and corner with [CrS6] octahedra. The [P2S7] unit is comprised of two [PS4] units sharing common corner. The ACrP2S7(A = K, Rb, Cs) structures are isostructural with RbVP2S7 and KMP2S7 (M = Cr, V and In). The classical charge valence if the compound can be written as [A+][Cr3+][[P5+]2[S2-]7 (A = K, Rb, Cs). Finally, the compound of Rb2CrP2S6 crystals have plate shape and dark brown color. Rb2CrP2S6 crystallizes in the space group Pbca. These [CrS6] octahedral units are linked by sharing three μ-S atoms of [P2S6]4− anions to form the infinite two-dimensional [CrP2∞2S6 −] layers. The classical charge valence of these compounds should be represented by [Rb+][Cr3+][P2S64-].
URI
https://dspace.ajou.ac.kr/handle/2018.oak/8495
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Graduate School of Ajou University > Department of Energy Systems > 3. Theses(Master)
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