College of Chemistry and Chemical Engineering , Qingdao University , Shandong 266071 , P.R. China.
College of Science , Hebei University of Science and Technology , Shijiazhuang , Hebei 050018 , P.R. China.
Inorg Chem. 2019 Mar 4;58(5):3527-3534. doi: 10.1021/acs.inorgchem.9b00101. Epub 2019 Feb 13.
Three zeolitic pentaborates (Hen)[BO(OH)] (1, en = ethylenediamine), (Hen)[Al(BO)] (2), (Hen)[NH(CH)][Al(BO)] (3) were solvothermally obtained by employing ethanediamine molecules as structure-directing agents (SDAs). The nonmetal borate of 1 features a noncentrosymmetric two-dimensional layered structure. Through introducing Al atoms as the linkers and regulating the reaction conditions of 1, two three-dimensional zeolitic open-framework aluminoborates, noncentrosymmetric (NCS) of 2 and centrosymmetric (CS) of 3, were achieved. Both 2 and 3 exhibit [Al(BO)] zeolitic frameworks based on the same fundamental building blocks (FBBs). However, the different arrangements between two FBBs result in 2 showing a NCS framework with dia topology, while 3 presents CS framework with cag topology. The flexibility of linkages modes of the FBBs as well as the unique structure-directing functions play crucial roles in the different formations. Powder second-harmonic generation (SHG) measurements revealed that acentric 1 and 2 possess nonlinear optical activity and 2 is type I phase-matchable with SHG responses of ∼1.0 time for KDP (KHPO). Infrared and UV-vis diffuse reflectance spectroscopy, along with electronic structure calculations, were also performed for the materials.
三种沸石五硼酸盐（Hen）[BO（OH）]（1，en=乙二胺）、（Hen）[Al（BO）]（2）、（Hen）[NH（CH）][Al（BO）]（3）通过使用乙二胺分子作为结构导向剂（SDAs），在溶剂热条件下得到。1 的非金属硼酸盐具有非中心对称的二维层状结构。通过引入 Al 原子作为连接体，并调节 1 的反应条件，实现了两种三维沸石开放骨架硼铝酸盐，非中心对称（NCS）的 2 和中心对称（CS）的 3。2 和 3 均基于相同的基本构筑块（FBBs）表现出[Al（BO）]沸石骨架。然而，两个 FBBs 之间的不同排列导致 2 呈现出具有 dia 拓扑的 NCS 骨架，而 3 呈现出具有 cag 拓扑的 CS 骨架。FBBs 的连接模式的灵活性以及独特的结构导向功能在不同的形成中起着关键作用。粉末二次谐波产生（SHG）测量表明，非中心对称的 1 和 2 具有非线性光学活性，并且 2 是与 SHG 响应相当的 I 型相位匹配材料，KDP（KHPO）的响应为 1.0 倍。还对材料进行了红外和紫外-可见漫反射光谱以及电子结构计算。
