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4성분계 크롬 Thiophosphate 계열 화합물의 합성·구조 및 특성

Synthesis and Characterization of Quaternary Chromium Thiophosphates

초록/요약

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-].

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목차

ABSTRACT
ABSTRACT(KOREA)
INTRODUCTION

CHAPTER Ι. Synthesis and Characterization of New Zero-dimensional Chromium Thiophosphates, Cs2CrPS6
1. Abstract
2. Experimental
Synthesis
Crystallographic studies
3. Result and discussion
4. Figures
5. Tables

CHAPTER Ⅱ. Synthesis and Characterization of New One-dimensional Chromium Thiophosphates, ACrPS5 (A = Rb, Cs)
1. Abstract
2. Experimental
Synthesis
Crystallographic studies
UV/Vis spectroscopy
3. Result and discussion
4. Figures
5. Tables

CHAPTER Ⅲ. Synthesis and Characterization of New Two-dimensional Chromium Thiophosphates, ACrP2S7 (A = K, Cs, Rb)
1. Abstract
2. Experimental
Synthesis
Crystallographic studies
Magnetic propertires
3. Result and discussion
4. Figures
5. Tables

CHAPTER ΙV. Synthesis and Characterization of New Two-dimensional Chromium Thiophosphates, RbCrP2S6
1. Abstract
2. Experimental
Synthesis
Crystallographic studies
3. Result and Discussion
4. Figures
5. Tables

Appendix. Synthesis and Structural Determination of a New Three-Dimensional Zirconium Germanium Sulfide, Rb2ZrGe5S13
1. Abstract
2. Experimental
Synthesis
crystallographic studies
UV/Vis spectroscopy
3. Result and Discussion
4. Figures
5. Tables

REFERENCE

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