Evenson C R, Dorhout P K
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.
Inorg Chem. 2001 Jun 4;40(12):2884-91. doi: 10.1021/ic000596r.
An alkali-metal sulfur reactive flux has been used to synthesize a series of quaternary rare-earth metal compounds. These include KLaP(2)S(6) (I), K(2)La(P(2)S(6))(1/2)(PS(4)) (II), K(3)La(PS(4))(2) (III), K(4)La(0.67)(PS(4))(2) (IV), K(9-x)La(1+x/3)(PS(4))(4) (x = 0.5) (V), K(4)Eu(PS(4))(2) (VI), and KEuPS(4) (VII). Compound I crystallizes in the monoclinic space group P2(1)/c with the cell parameters a = 11.963(12) A, b = 7.525(10) A, c = 11.389(14) A, beta = 109.88(4) degrees, and Z = 4. Compound II crystallizes in the monoclinic space group P2(1)/n with a = 9.066(6) A, b = 6.793(3) A, c = 20.112(7) A, beta = 97.54(3) degrees, and Z = 4. Compound III crystallizes in the monoclinic space group P2(1)/c with a= 9.141(2) A, b = 17.056(4) A, c = 9.470(2) A, beta = 90.29(2) degrees, and Z = 4. Compound IV crystallizes in the orthorhombic space group Ibam with a = 18.202(2) A, b = 8.7596(7) A, c = 9.7699(8) A, and Z = 4. Compound V crystallizes in the orthorhombic space group Ccca with a = 17.529(9) A, b = 36.43(3) A, c = 9.782(4) A, and Z = 8. Compound VI crystallizes in the orthorhombic space group Ibam with a = 18.29(5) A, b = 8.81(2) A, c= 9.741(10) A, and Z = 4. Compound VII crystallizes in the orthorhombic space group Pnma with a = 16.782(2) A, b = 6.6141(6) A, c = 6.5142(6) A, and Z = 4. The sulfur compounds are in most cases isostructural to their selenium counterparts. By controlling experimental conditions, these structures can be placed in quasi-quaternary phase diagrams, which show the reaction conditions necessary to obtain a particular thiophosphate anionic unit in the crystalline product. These structures have been characterized by Raman and IR spectroscopy and UV-vis diffuse reflectance optical band gap analysis.
一种碱金属硫反应性助熔剂已被用于合成一系列四元稀土金属化合物。这些化合物包括KLaP₂S₆（I）、K₂La(P₂S₆)₁/₂(PS₄)（II）、K₃La(PS₄)₂（III）、K₄La₀.₆₇(PS₄)₂（IV）、K₉₋ₓLa₁₊ₓ/₃(PS₄)₄（x = 0.5）（V）、K₄Eu(PS₄)₂（VI）和KEuPS₄（VII）。化合物I结晶于单斜空间群P2₁/c，晶胞参数a = 11.963(12) Å，b = 7.525(10) Å，c = 11.389(14) Å，β = 109.88(4)°，Z = 4。化合物II结晶于单斜空间群P2₁/n，a = 9.066(6) Å，b = 6.793(3) Å，c = 20.112(7) Å，β = 97.54(3)°，Z = 4。化合物III结晶于单斜空间群P2₁/c，a = 9.141(2) Å，b = 17.056(4) Å，c = 9.470(2) Å，β = 90.29(2)°，Z = 4。化合物IV结晶于正交空间群Ibam，a = 18.202(2) Å，b = 8.7596(7) Å，c = 9.7699(8) Å，Z = 4。化合物V结晶于正交空间群Ccca，a = 17.529(9) Å，b = 36.43(3) Å，c = 9.782(4) Å，Z = 8。化合物VI结晶于正交空间群Ibam，a = 18.29(5) Å，b = 8.81(2) Å，c = 9.741(10) Å，Z = 4。化合物VII结晶于正交空间群Pnma，a = 16.782(2) Å，b = 6.6141(6) Å，c = 6.5142(6) Å，Z = 4。这些硫化合物在大多数情况下与其硒对应物同构。通过控制实验条件，这些结构可以被置于准四元相图中，该相图显示了在晶体产物中获得特定硫代磷酸根阴离子单元所需的反应条件。这些结构已通过拉曼光谱、红外光谱和紫外可见漫反射光学带隙分析进行了表征。
