Wang Wen-Wen, Xu Xiang, Kong Jin-Tao, Mao Jiang-Gao
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou 350002, People's Republic of China.
College of Chemistry, Fuzhou University , Fuzhou 350108, People's Republic of China.
Inorg Chem. 2018 Jan 2;57(1):163-174. doi: 10.1021/acs.inorgchem.7b02317. Epub 2017 Dec 14.
Using hydrothermal reactions, three series of rare-earth borate-sulfates, namely, RE(SO)B(OH) (RE = La (1), Sm (2), Eu (3)), RE(SO)B(OH) (RE = Pr (4), Nd (5), Sm (6), Eu (7), Gd (8)), and RE(SO)B(OH)·HO (RE = Tb (9), Dy (10), Ho (11), Er (12), Tm (13), Yb (14), Lu (15), Y (16)), have been synthesized, which represent the first rare-earth borate-sulfate mixed-anion compounds. All these compounds possess the same fundamental building anionic units of SO and B(OH) tetrahedra; however, they exhibit three different types of two-dimensional (2D) layered structures composed of 1D RE-B-O and RE-S-O chains. The rare-earth borate chains are similar in all compounds, while the rare-earth sulfate chains differ in each type of compound due to the various coordination modes of sulfate groups. On the basis of the measured UV-vis diffuse reflectance spectra, the optical band gaps of compounds 2, 3, 6, and 7 are estimated to be 4.66, 4.53, 4.62, and 4.50 eV, respectively. Luminescence studies show that compounds 2, 3, 6, and 7 exhibit strong emission in the orange or red regions. Furthermore, thermal analysis and magnetic susceptibility measurements for these four representative compounds have also been performed.
通过水热反应，合成了三个系列的稀土硼酸盐 - 硫酸盐，即RE(SO₄)B(OH)₄₃（RE = La (1)，Sm (2)，Eu (3)）、RE₂(SO₄)₃[B(OH)₄]₂(H₂O)₄（RE = Pr (4)，Nd (5)，Sm (6)，Eu (7)，Gd (8)）以及RE₂(SO₄)₃[B(OH)₄]₂(H₂O)₄·H₂O（RE = Tb (9)，Dy (10)，Ho (11)，Er (12)，Tm (13)，Yb (14)，Lu (15)，Y (16)），它们代表了首批稀土硼酸盐 - 硫酸盐混合阴离子化合物。所有这些化合物都具有相同的基本构建阴离子单元SO₄²⁻和B(OH)₄⁻四面体；然而，它们呈现出由一维RE - B - O和RE - S - O链组成的三种不同类型的二维（2D）层状结构。所有化合物中的稀土硼酸盐链相似，而由于硫酸根基团的各种配位模式，每种类型化合物中的稀土硫酸盐链有所不同。基于测得的紫外 - 可见漫反射光谱，化合物2、3、6和7的光学带隙分别估计为4.66、4.53、4.62和4.50 eV。发光研究表明，化合物2、3、6和7在橙色或红色区域表现出强烈发射。此外，还对这四种代表性化合物进行了热分析和磁化率测量。
