Shen Yaoguo, Huang Longjie, Wang Zhifeng, Zhou Yingwu, Xue XiaoLing, Lin Hong, Yan Renwen, Zhao Sangen, Luo Junhua
College of Physics and Electronic Information Engineering, Minjiang University, Fuzhou, Fujian 350108, China.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
Inorg Chem. 2022 Mar 14;61(10):4468-4475. doi: 10.1021/acs.inorgchem.1c04026. Epub 2022 Mar 1.
SO tetrahedral groups have weak polarization anisotropy, which thus results in the small birefringence of sulfates. Here, we report new sulfate CsY(SO)·4HO with unprecedented birefringence among deep-ultraviolet (deep-UV) sulfates. Its single crystal (10 mm × 3.5 mm × 1.5 mm) was simply grown by an aqueous solution evaporation technique, and it features a rare layered structure composed of YO polyhedra, SO tetrahedra, and HO molecules. Interestingly, each SO group donates two oxygen atoms to edge-share with one adjacent YO polyhedron and thus causes severe distortion of these groups. The characteristic edge-sharing mode gives CsY(SO)·4HO a large birefringence of ∼0.045@546 nm, which is the maximum among deep-UV sulfates and phosphates with similar non-π-conjugated anionic groups. The ultraviolet-visible-near-infrared diffuse reflection and transmission spectra, infrared spectrum, thermal stability, and theoretical calculations are also presented. The fascinating results will improve our understanding of sulfates and may provide useful insights into the exploration of deep-UV sulfates with large birefringence.
因此，四面体基团具有较弱的极化各向异性，这导致了硫酸盐的双折射较小。在此，我们报道了一种新型硫酸盐CsY(SO₄)₂·4H₂O，在深紫外（deep-UV）硫酸盐中具有前所未有的双折射。其单晶（10 mm × 3.5 mm × 1.5 mm）通过水溶液蒸发技术简单生长而成，其特征是具有由YO₆多面体、SO₄四面体和H₂O分子组成的罕见层状结构。有趣的是，每个SO₄基团贡献两个氧原子与一个相邻的YO₆多面体边缘共享，从而导致这些基团严重扭曲。这种独特的边缘共享模式赋予CsY(SO₄)₂·4H₂O在546 nm处约为0.045的大双折射，这是具有类似非π共轭阴离子基团的深紫外硫酸盐和磷酸盐中的最大值。还给出了紫外-可见-近红外漫反射和透射光谱、红外光谱、热稳定性以及理论计算结果。这些引人入胜的结果将增进我们对硫酸盐的理解，并可能为探索具有大双折射的深紫外硫酸盐提供有用的见解。
