CsBa2ScB8O16:首例结构中同时含有零维[B3O6]基元和一维B—O链的稀土硼酸盐

摘要/Abstract

摘要： 利用高温溶液法合成了首例结构中同时含有零维[B₃O₆]基元和一维B—O链的稀土硼酸盐晶体CsBa₂ScB₈O₁₆,该晶体属于三斜晶系,空间群为P1,晶胞参数为a=6.698 5 Å,b=7.216 Å,c=14.798 Å,α=97.563°,β=95.226°,γ=95.546°,Z=2。该晶体中的[BO₃]与[B₄O₉]基元通过共享氧原子连接形成一维[B₅O₁₀]_∞链,[Sc(1)O₆]八面体与一维[B₅O₁₀]_∞链通过共享氧原子形成二维[Sc(1)(B₄O₉)]_∞层,层间由[Sc(2)O₆]八面体连接形成Sc—B—O三维框架。孤立的[B₃O₆]基元与Cs⁺、Ba²⁺填充在三维孔道内维持电荷平衡。为了进一步探索CsBa₂ScB₈O₁₆结构的新颖性,将该晶体与其他含有碱金属或碱土金属的稀土硼酸进行比较,讨论了阳离子与硼的摩尔比(n(A)/n(B))对B—O基元的聚合度及B—O阴离子框架维度的影响。此外,对化合物进行了红外光谱、紫外-可见-近红外漫反射光谱,以及热学行为等表征测试,并基于第一性原理计算对化合物微观电子层面进行了计算分析。结果表明CsBa₂ScB₈O₁₆的紫外截止边小于190 nm,双折射为0.072@1 064 nm,其光学特性主要由[B₃O₆]基元、[B₅O₁₀]基元和[ScO₆]多面体贡献。

关键词: 稀土硼酸盐, 高温溶液法, 晶体结构, B—O框架, 第一性原理计算, 双折射

Abstract: The first rare-earth borate crystal CsBa₂ScB₈O₁₆ with both zero-dimensional [B₃O₆] units and one-dimensional B—O chain structures has been synthesized by the high-temperature solution method. It crystallizes in the triclinic crystal system with the P1 space group, with lattice parameters of a=6.698 5 Å, b=7.216 Å, c=14.798 Å, α=97.563°, β=95.226°, γ=95.546°, Z=2. In this compound, [BO₃] and [B₄O₉] units are connected by sharing oxygen atoms to form a one-dimensional chain [B₅O₁₀]_∞. Octahedrally coordinated [Sc(1)O₆] groups and the one-dimensional chain [B₅O₁₀]_∞ are further connected by sharing oxygen atoms to form two-dimensional layer [Sc(1)(B₄O₉)]_∞. Interlayers are linked by octahedrally coordinated [Sc(2)O₆] groups, which share oxygen atoms to form a three-dimensional Sc—B—O framework. Isolated [B₃O₆] units are filled in the three-dimensional channels with Cs⁺ and Ba²⁺ to balance the charges. In order to further explore the novelty of the structure of CsBa₂ScB₈O₁₆, we compared it with other rare-earth borates containing alkali or alkaline-earth metals, and discuss the effect of the cation-to-boron molar ratio (n(A)/n(B)) on the degree of polymerization of B—O units, as well as the dimensionality of the B—O anion framework. Furthermore, the first-principles calculations, infrared spectrum, UV-vis-NIR diffuse reflectance spectrum and the thermal analysis of the compounds have also been performed. Property measurements show that CsBa₂ScB₈O₁₆ exhibits short UV absorption edge (＜190 nm) and moderate birefringence (0.072@1 064 nm). The optical properties of the compound are mainly contributed by the [B₃O₆], [B₅O₁₀] units, and [ScO₆] octahedra.

Key words: rare-earth borate, high-temperature solution method, crystal structure, B—O framework, first-principles calculation, birefringence

中图分类号:

O734

焦思慧, 吴红萍, 俞洪伟. CsBa₂ScB₈O₁₆:首例结构中同时含有零维[B₃O₆]基元和一维B—O链的稀土硼酸盐[J]. 人工晶体学报, 2024, 53(9): 1550-1559.

JIAO Sihui, WU Hongping, YU Hongwei. CsBa₂ScB₈O₁₆: the First Rare-Earth Borate Simultaneously Containing Zero-Dimensional [B₃O₆] Units and One-Dimensional B—O Chains[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(9): 1550-1559.

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CsBa₂ScB₈O₁₆:首例结构中同时含有零维[B₃O₆]基元和一维B—O链的稀土硼酸盐

CsBa₂ScB₈O₁₆: the First Rare-Earth Borate Simultaneously Containing Zero-Dimensional [B₃O₆] Units and One-Dimensional B—O Chains

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