Qiu Haotian, Li Fuming, Jin Congcong, Yang Zhihua, Li Junjie, Pan Shilie, Mutailipu Miriding
Research Center for Crystal Materials, Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, 830011, P. R. China.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Angew Chem Int Ed Engl. 2024 Jan 22;63(4):e202316194. doi: 10.1002/anie.202316194. Epub 2023 Dec 20.
Borate crystals can be chemically and functionally modified by the fluorination strategy, which encourages the identification of emerging fluorooxoborates with a structure and set of characteristics not seen in any other oxide parents. However, the bulk of fluorooxoborates have been found accidentally, rational methods of synthesis are required, particularly for the infrequently occurring poly-fluorinated components. Herein, we reported the use of bifluoride salts as a potent source of fluorine to prepare fluorooxoborates that contain rarely tri-fluorinated [BF X] (X=O and CH ) tetrahedra and eleven compounds were found. We identified the optical properties of the organofluorinated group [CH BF ] and their potential for nonlinear optics for the first time. Among these, two non-centrosymmetric components hold potential for the production of 266 nm harmonic coherent light for nonlinear optics, and more crucially, have the benefit of growing large size single crystals. Our study establishes experimental conditions for the coexistence of the diverse functional groups, enabling the production of poly-fluorinated optical crystals.
硼酸盐晶体可以通过氟化策略进行化学和功能改性，这有助于鉴定出具有独特结构和特性的新型氟氧化硼酸盐，这些特性在其他任何氧化物母体中都未曾见过。然而，大多数氟氧化硼酸盐都是偶然发现的，因此需要合理的合成方法，特别是对于不常见的多氟化物成分。在此，我们报道了使用氟氢酸盐作为有效的氟源来制备含有罕见的三氟代[BFX]（X = O和CH）四面体的氟氧化硼酸盐，并发现了11种化合物。我们首次确定了有机氟基团[CHBF]的光学性质及其在非线性光学方面的潜力。其中，两种非中心对称成分具有产生用于非线性光学的266nm谐波相干光的潜力，更重要的是，它们具有生长出大尺寸单晶的优势。我们的研究建立了多种官能团共存的实验条件，从而能够制备多氟光学晶体。
