Tailoring Hybrid Aluminoborate Frameworks by Incorporating Multicomponent Cadmium-Amine Complexes with Various...

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 Cd²⁺ 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)_0.5][AlB₅O₁₀] (1a; its analogue with discrete complex [Cd(en)(dien)H₂O][AlB₅O₁₀] is denoted as 1b), [Cd(1,2-dap)_1.5(1,4-dabH)_0.5]{Al[B₅O₈(OH)₂](B₅O₁₀)_0.5} (2), and [Cd(en)(1,3-dap)][AlB₅O₁₀] (3) feature open frameworks (1a, 1b, and 3) or a sandwich-like porous layer (2) that are constructed by AlO₄ tetrahedra and [B₅O₁₀]^5-/[B₅O₈(OH)₂]^3- 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 BO₃ and AlO₄, (ii) the same AlO₄, or (iii) the same BO₃. 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 Cd²⁺ complexes endows these aluminoborate materials with photoluminescence function. Compound 3 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.