Yan Ziting, Fan Jinbin, Chu Dongdong, Yang Zhihua, Lu Juanjuan, Pan Shilie, Zhang Min
Research Center for Crystal Materials, State Key Laboratory of Functional Materials and Devices for Special Environmental Conditions, Xinjiang Key Laboratory of Functional Crystal Materials, Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, 40-1 South Beijing Road, Urumqi 830011, China.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
Inorg Chem. 2024 Sep 2;63(35):16461-16469. doi: 10.1021/acs.inorgchem.4c02728. Epub 2024 Aug 21.
Borates, due to their structural chemistry diversity and exceptional performance, are premier material systems for investigating UV optical crystals. The B-O anionic groups with high polymerization (B ≥ 6) are much less in the borate-based system, which is worthy of further research. Herein, cations with different radii and proportions are introduced to borate system, and two new highly polymerized borates, LiNaCaBOFCl (LNCBFC) and LiNaBO (LNBO) were designed and synthesized successfully. LNCBFC possesses commonly isolated high-symmetry [BO] groups, while the structure of LNBO contains an unprecedented [BO] chain constructed by [BO] groups. Owing to the orientation of the functional motifs in the chain structure, LNBO displays an enhanced birefringence, which is about 25 × higher than that of LNCBFC and retains a short UV cutoff edge (< 200 nm). Even more significantly, a discussion of the cationic modulation of [BO]-based compounds and the patterns of isolated [BO] motifs consisting of B-O rings was carried out by reviewing previous studies and existing borates. This work puts forward a decent structure design and property regulation strategy for highly polymerized borates.
硼酸盐因其结构化学的多样性和卓越性能，是研究紫外光学晶体的首要材料体系。在硼酸盐体系中，具有高聚合度（B≥6）的B - O阴离子基团较少，这值得进一步研究。在此，将不同半径和比例的阳离子引入硼酸盐体系，成功设计并合成了两种新型的高聚合硼酸盐LiNaCaBOFCl（LNCBFC）和LiNaBO（LNBO）。LNCBFC具有常见的孤立高对称[BO]基团，而LNBO的结构包含由[BO]基团构建的前所未有的[BO]链。由于链结构中功能基序的取向，LNBO表现出增强的双折射，比LNCBFC高约25倍，并且保持较短的紫外截止边（<200 nm）。更重要的是，通过回顾以往的研究和现有的硼酸盐，对基于[BO]的化合物的阳离子调制以及由B - O环组成的孤立[BO]基序的模式进行了讨论。这项工作为高聚合硼酸盐提出了一种合理的结构设计和性能调控策略。
