Martin Benjamin R, Dorhout Peter K
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.
Inorg Chem. 2004 Jan 12;43(1):385-91. doi: 10.1021/ic034724y.
In this work, we used the molten chalcogenide flux synthetic method to form an analogous series of alkali samarium selenogermanates, with the general formula ASmGeSe(4) (A = K, Rb, Cs). Using a constant reactant stoichiometry, we relate the monoclinic KLaGeSe(4) structure type to the orthorhombic CsSmGeS(4) structure type. KSmGeSe(4) [in space group P2(1) with cell parameters a = 6.774(1) A, b = 6.994(1) A, c = 8.960(2) A, beta = 108.225(3) degrees, and V = 403.2(1) A(3) (Z = 2)], RbSmGeSe(4) [in space group P2(1)2(1)2(1) with cell parameters a = 6.7347(8) A, b = 7.0185(9) A, c = 17.723(2) A, and V = 837.7(2) A(3) (Z = 4)], and CsSmGeSe(4) [in space group P2(1)2(1)2(1) with cell parameters a = 6.707(2) A, b = 7.067(2) A, c = 18.334(6) A, and V = 869.1(5) A(3) (Z = 4)] were formed under identical synthetic conditions by changing the identity of the alkali ion from K to Rb or Cs, respectively. Additionally, with the substitution of sodium into the reaction, a triclinic structure with the approximate formula NaSmGeSe(4) was found with the cell parameters a = 6.897(2) A, b = 9.919(2) A, c = 11.183(2) A, alpha = 84.067(4) degrees, beta = 88.105(4) degrees, gamma = 73.999(4) degrees, and V = 731.5(3) A(3). In addition to single-crystal diffraction, Raman and diffuse reflectance UV-visible spectroscopic measurements have been used to characterize these compounds.
在本工作中，我们采用熔融硫属化物助熔剂合成法，制备了一系列通式为ASmGeSe₄（A = K、Rb、Cs）的碱金属钐硒锗酸盐类似物。通过保持反应物化学计量比恒定，我们将单斜晶系的KLaGeSe₄结构类型与正交晶系的CsSmGeS₄结构类型联系起来。通过分别将碱金属离子从K变为Rb或Cs，在相同的合成条件下制备出了KSmGeSe₄[空间群为P2(1)，晶胞参数a = 6.774(1) Å，b = 6.994(1) Å，c = 8.960(2) Å，β = 108.225(3)°，V = 403.2(1) ų（Z = 2）]、RbSmGeSe₄[空间群为P2(1)2(1)2(1)，晶胞参数a = 6.7347(8) Å，b = 7.0185(9) Å，c = 17.723(2) Å，V = 837.7(2) ų（Z = 4）]和CsSmGeSe₄[空间群为P2(1)2(1)2(1)，晶胞参数a = 6.707(2) Å，b = 7.067(2) Å，c = 18.334(6) Å，V = 869.1(5) ų（Z = 4）]。此外，在反应中引入钠后，发现了一种近似组成为NaSmGeSe₄的三斜晶系结构，其晶胞参数a = 6.897(2) Å，b = 9.919(2) Å，c = 11.183(2) Å，α = 84.067(4)°，β = 88.105(4)°，γ = 73.999(4)°，V = 731.5(3) ų。除了单晶衍射外，还利用拉曼光谱和漫反射紫外 - 可见光谱测量对这些化合物进行了表征。
