Five aluminoborates Al[B(5)O(10)] x H(2)dab x 2 H(2)O (1), [Al(B(4)O(9))(BO)] x H(2)en (2), [Al(B(4)O(9))(BO)] x H(2)dap (3), K(2)Al[B(5)O(10)] x 4 H(2)O (4), and (NH(4))(2)Al[B(5)O(10)] x 4 H(2)O (5) have been synthesized under hydrothermal conditions and characterized by means of elemental analysis, IR, TG analysis, MAS NMR, UV-vis and fluorescence spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction, and NLO determination. The structure 1 comprises of AlO(4) tetrahedra and B(5)O(10) clusters and contains 12-, 11-, and 8-MR 3D-intersecting channels with a CrB(4) topological net. Structures 2 and 3 are both constructed from the same AlB(5)O(13) clusters and exhibit a six-connected framework with 4(12)6(3) topology. Structures 4 and 5 are isomorphous and are composed of AlO(4) tetrahedra and B(5)O(10) clusters that possess odd 11-MR channels and 8-MR helical channels. Structures 2-5 crystallized in an acentric structure and presented good SHG properties. UV-vis spectral investigation indicates that they are wide-band-gap semiconductors. The electronic structure calculations for the compounds also have been performed.

A series of open-framework aluminoborates (ABOs) [M(dien)(2)][AlB(6)O(11)(OH)] (M=Co (I a), Ni (I b), Cd (I c), Zn (I d); dien=diethylenetriamine) and [M(en)(3)][AlB(7)O(12)(OH)(2)] (H(2)O)(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 AlO(4) tetrahedra and B(6)O(11)(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 AlO(4) tetrahedra, chainlike B(4)O(6)(OH)(2) tetramer, and crablike B(6)O(12) 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.