Tailoring Hybrid Aluminoborate Frameworks by Incorporating Multicomponent Cadmium–Amine Complexes with Various Conformations

Abstract

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.

Two Acentric Aluminoborates Incorporated d10 Cations: Syntheses, Structures, and Nonlinear Optical Properties

“…Such structures composed of B 5 O 10 clusters and AlO 4 units are common, but the different expansion modes causes each framework to have unique structural features. In the previous reports, 3D ABO frameworks display different four-connected networks such as dia , sra , crb , and cag and possess different types of channels from 6- to 14-MRs. − So far, the unc -type topology in 2 was first found in ABOs.…”

Two pairs of chiral YbIII enantiomers presenting distinct NIR luminescence and circularly polarized luminescence performances with giant differences in second-harmonic generation responses

“…In order to confirm this fact, DFT calculations on the dipole moments of D-1 and D-2 were performed using the Gaussian 09 package, and the results unveil that the dipole moment ( μ total = 7.14 D) of D-1 is much larger than that of D-2 ( μ total = 2.73 D) (Table S7†). Moreover, as shown in Table 1, the SHG intensities of D-1/L-1 are much larger than those of most reported SHG-active complexes, such as 1D chiral Cu( ii ) enantiomers with L R /L S ligands, 81 [Dy(dma) 5 ][W(CN) 8 ], 110 chiral R / S -FeNb enantiomers, 111 chiral YbZn 2 enantiomers, 112 chiral L/D-ZnBr 3 enantiomers, 113 (CASD) 2 MnBr 4 , 114 [(DPA)(18-crown-6)]ClO 4 , 115 chiral 2D Ag( i ) enantiomers, 80 a chiral Cu( i ) complex, 116 N*[MnCr], 117 C 2 H 10 N 2 ·Mg(H 2 PO 3 ) 2 (C 2 O 4 ), 118 [C(NH 2 ) 3 ] 2 Zn(CO 3 ) 2 , 119 ionic 1D chiral Cu( ii ) enantiomers with L R /L S ligands, 72 [Cd(en)-(1,3-dap)][AlB 5 O 10 ], 120 (morpholinium) 2 Cd 2 Cl 6 , 121 (C 4 H 10 NO)PbBr 3 , 122 [C(NH 2 ) 3 ] 3 AsO 4 ·2H 2 O, 123 and (Hdabco + )(CF 3 COO − ), 124 but slightly smaller than those of some complexes, such as a YbSe complex 125 and [(CH 3 ) 3 NCH 2 CHCH 2 ]FeCl 4 . 126 More remarkably, the SHG intensities of D-1/L-1 are even more than twice those of inorganic SHG-active materials, for example KTOH 127 and CKBFI.…”

Structural Regulations of Layered Borates: From Centric Layers to Chiral Porous Layers

“…Under hydro­(solvo)­thermal conditions, different reacting conditions have different influences on the formation of borate frameworks. As structural directing agents (SDAs), guest species including cations and anions have decisive roles in the formation of the frameworks and symmetries, which correspond to the optical properties. − Host–guest symmetry and charge matching in borates’ systems were proposed based on the different effects of SDAs . In order to increase the possibility of acentric frameworks, alkali and alkaline-earth metal cations have priority in all kinds of SDAs for their spherical coordination geometries, which would greatly reduce the influences from guest templates on acentric frameworks.…”