A Series of Open-Framework Aluminoborates Templated by Transition-Metal Complexes

摘要

A series of open-framework aluminoborates (ABOs) [M(dien)₂][AlB₆O₁₁(OH)] (M=Co (I a), Ni (I b), Cd (I c), Zn (I d); dien=diethylenetriamine) and [M(en)₃][AlB₇O₁₂(OH)₂] (H₂O)_0.25 (M=Co (II a), Ni (II b); en=ethylenediamine) have been made under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, UV/Vis and fluorescence spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction, and nonlinear optical determination. These compounds were classified as two structural types: Type I (I a–d) contains AlO₄ tetrahedra and B₆O₁₁(OH) clusters, which link to form a new 3D framework with 7-/9-ring helical channels and large 13-ring channels; whereas type II (II a,b) is composed of AlO₄ tetrahedra, chainlike B₄O₆(OH)₂ tetramer, and crablike B₆O₁₂ clusters, which interconnect to form other new 3D frameworks with 8-ring helical channels, rare 16-ring double-helical channels, and larger odd 15-ring channels. These compounds represent the first examples of 3D ABOs templated by transition-metal complexes (TMCs). I c,d present good second harmonic generation (SHG) properties. UV/Vis spectral investigation indicates that I a–d and II a,b are wide-band-gap semiconductors.