A Series of Aluminoborates Templated or Supported by Zinc-Amine Complexes.

A series of open-framework aluminoborates (ABOs), namely, [Zn2 (en)5 ][Al2 B10 O20 ] (1), [Zn(en)(dien)][AlB5 O10 ] (2), [Zn(en)3 ][AlB7 O12 (OH)2 ] (3), [Zn(en)2 ][AlB5 O10 ] (4), K7 {AlO0.5 [BO2 (OH)]Zn@[B12 O21 (OH)3 ]}⋅H2 O (5) (en=ethylenediamine, dien=diethylenetriamine) have been made under mild solvothermal conditions and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR and UV/Vis spectroscopy, thermogravimetric analysis, and nonlinear optical determination. They were classified as two types: Compounds 1-4 contain intersecting channels and exhibit various 4-connected nets built by AlO4 tetrahedra and oxo boron clusters, zinc-amine complexes act as the templates (1-3) or directly bond to the walls of the ABO (4); compound 5 exhibits a double-layer structure made by nanosized [BO2 (OH)]Zn@[B12 O21 (OH)3 ] ({BZn@B12 }) clusters with Al2 O7 dimers, the channels are within the layer. The second harmonic generation (SHG) measurement shows that the SHG responses of 1-3 are about 2.5, 1.6, and 0.5 times that of KH2 PO4 . Compounds 1-2 are type I phase-matchable materials. UV/Vis spectroscopy indicates that compounds 1-5 are wide-band-gap semiconductors.