Wei Qi, Sun Shi-Jia, Zhang Jie, Yang Guo-Yu
MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, P. R. China.
Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China.
Chemistry. 2017 Jun 1;23(31):7614-7620. doi: 10.1002/chem.201701222. Epub 2017 May 15.
Two novel alkali/alkaline-earth borates, Ba [B O (OH) ] (H BO ) (1) and Li MAlB O (M=Ba, Sr, Ca) (2 a-c), with 1D and 3D structures have been made hydrothermally and characterized. 1 features a rare 1D anionic chain built by hexaborate clusters of B O (OH) ; each made of six BO /BO (OH) tetrahedra. The anionic chains are embedded in the channels of a Ba -based wheel-cluster open-framework. On the basis of the structural analyses of 1, by incorporating Al atoms as the linkers and tuning the reaction conditions, the novel anhydrous 3D aluminoborates (ABOs) 2 a-c have been successfully obtained, constructed from B O -based cluster chains and AlO octahedra. The 3D ABO framework and 3D Ba-O-Li network are interpenetrated to give a final dense structure. The study not only realized the expansion of the structure from the 1D chain of 1 to the 3D dense ABOs 2 a-c, but also obtained the first 3D AlO -containing ABOs made under hydrothermal conditions. Different from the previously known 4-connected zeolite-type ABOs, alternately arranged from AlO tetrahedra and oxo-boron clusters, the AlO octahedra in 2 a-c as the linkers join to six 1D B O -based cluster chains to produce 3D ABOs. The optical diffuse reflectance spectra reveal that 2 a-c have wide range transparency. In addition, the thermal property analysis proves that 2 a-c are congruently melting compounds and possess high thermostability.
通过水热法制备并表征了两种具有一维和三维结构的新型碱金属/碱土金属硼酸盐,BaB₃O₃(OH)₃(1)和LiMAlB₃O₆(M = Ba、Sr、Ca)(2a - c)。化合物1具有由B₃O₃(OH)₃六硼酸盐簇构建的罕见一维阴离子链;每个簇由六个BO₃/BO(OH)₄四面体组成。阴离子链嵌入到基于Ba的轮簇开放框架的通道中。基于对化合物1的结构分析,通过引入Al原子作为连接体并调整反应条件,成功获得了由B₃O₃基簇链和AlO₆八面体构成的新型无水三维铝硼酸盐(ABOs)2a - c。三维ABO框架和三维Ba - O - Li网络相互贯穿形成最终的致密结构。该研究不仅实现了结构从化合物1的一维链扩展到三维致密ABOs 2a - c,还获得了首例在水热条件下制备的含AlO₆的三维ABOs。与先前已知的由AlO₄四面体和氧硼簇交替排列而成的4连接沸石型ABOs不同,化合物2a - c中的AlO₆八面体作为连接体与六条一维B₃O₃基簇链相连,形成三维ABOs。光学漫反射光谱表明,2a - c具有宽范围的透明度。此外,热性质分析证明,2a - c是一致熔融化合物,具有高的热稳定性。