Cheng Lin, Xiong Xiao-Yun, Zhao Yi-Ming, Wang Ying, Wu Qiu-Ying, Wang Kai-Yao
College of Chemistry, Tianjin Normal University, Tianjin 300387, P.R. China.
Tianjin Key Laboratory of Advanced Functional Porous Materials, Institute for New Energy Materials and Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, P.R. China.
Inorg Chem. 2022 Aug 1;61(30):11675-11686. doi: 10.1021/acs.inorgchem.2c01259. Epub 2022 Jul 18.
Inorganic-organic hybrid aluminoborates represent a subclass of porous materials, which rely on effective construction method and structure-directing agents. Herein, we prepared a series of hybrid aluminoborates through covalent decoration of unsaturated Cd complexes, whose formation take advantage of chelating amine and long-chain diamine as mixed ligands. These isolated compounds, that is, [Cd(en)(1,4-dab)][AlBO] (; its analogue with discrete complex [Cd(en)(dien)HO][AlBO] is denoted as ), [Cd(1,2-dap)(1,4-dabH)]{AlBO(OH)} (), and [Cd(en)(1,3-dap)][AlBO] () feature open frameworks (, , and ) or a sandwich-like porous layer () that are constructed by AlO tetrahedra and [BO]/[BO(OH)] clusters. However, they exhibit different structural features in interconnection, channel environment, and topology as a result of diversified interactions between unsaturated complexes and aluminoborate frameworks, that is, through forming two Cd-O bonds with (i) a pair of neighboring BO and AlO, (ii) the same AlO, or (iii) the same BO. The variation in connection mode exerts essential influence on binding effects and steric hindrance that are reflected by changes in interatomic distance, bond angle, window configuration, and interlinkage of units. In addition, the incorporation of unsaturated Cd complexes endows these aluminoborate materials with photoluminescence function. Compound with a noncentrosymmetric structure exhibits second harmonic generation (SHG) response approximately 0.7 times that of KDP. The preparation strategy for hybrid aluminoborates proposed here combines well molecular design with templating assembly, whose synergistic effect would be crucial for drawing a rational pathway for inorganic synthesis, especially with focus on structural and functional innovation.
无机-有机杂化铝硼酸盐是多孔材料的一个子类，其依赖于有效的构建方法和结构导向剂。在此，我们通过不饱和镉配合物的共价修饰制备了一系列杂化铝硼酸盐，其形成利用螯合胺和长链二胺作为混合配体。这些孤立的化合物，即[Cd(en)(1,4-dab)][AlBO]（；其具有离散配合物[Cd(en)(dien)HO][AlBO]的类似物记为）、[Cd(1,2-dap)(1,4-dabH)]{AlBO(OH)}（）和[Cd(en)(1,3-dap)][AlBO]（）具有开放框架（、和）或由AlO四面体和[BO]/[BO(OH)]簇构建的三明治状多孔层（）。然而，由于不饱和配合物与铝硼酸盐框架之间的多样化相互作用，即通过与（i）一对相邻的BO和AlO、（ii）相同的AlO或（iii）相同的BO形成两个Cd-O键，它们在互连、通道环境和拓扑结构上表现出不同的结构特征。连接方式的变化对结合效果和空间位阻产生重要影响，这通过原子间距离、键角、窗口构型和单元间连接的变化得以体现。此外，不饱和镉配合物的引入赋予这些铝硼酸盐材料光致发光功能。具有非中心对称结构的化合物表现出约为KDP的0.7倍的二次谐波产生（SHG）响应。这里提出的杂化铝硼酸盐的制备策略将分子设计与模板组装很好地结合起来，其协同效应对于绘制无机合成的合理途径至关重要，特别是在结构和功能创新方面。
