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

Abstract

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.

A Series of Aluminoborates Templated or Supported by Zinc–Amine Complexes

“…Al 3 + ions may adopt different coordination geometries, such as AlO 4 tetrahedra, AlO 5 square pyramids, and AlO 6 octahedra. ABOs usually have four-connected zeolite topologies constructed by corner-sharing AlO 4 tetrahedra and oxo boron clusters under hydro(solvo)thermalc ondition (denoted as FJ-n), [14,15] [13c] The distinct structural type of ABOs between FJ-n and PKU-n may be attributedt od ifferent synthetic methods. The crystalline FJ-n species were made under solvothermal conditions by using aminesa st emplates, whereas the PKU-n species were made in boric acid flux without any organic template.…”

“…[6,13] Recently,w eh ave focusedo nt he hydro(solvo)thermal synthesis of open-framework ABOs using Al(iPrO) 3 as Al source, which promotes the growth of good-qualitys ingle crystalsa nd has led to greata dvances in systemso fi norganic cation-,o rganic amine-, and metal complex-templated ABOs. [14,15] These open-framework materials integrate the uniform porosity of zeolites with the extraordinaryo ptical properties of metal borates.…”

Linear and nonlinear optical properties of aluminum borate crystal Al5BO9: Experiment and calculation

“…1, which means that it is feasible to obtain borates with isolated BO 3 groups by increasing the proportion of cations in experiments. It is noteworthy that the introduction of cations with strong bonding (such as Be 21 , Al 31 , Mg 21 , Zn 21 , Si 41 , etc) 9,10,13,[17][18][19]21 can inhibit the polymerization of B-O groups. Hence, the UV-favorable system, Al-B-O, was chosen and anticipated to find new borate with excellent NLO property.…”

A new 1-D In–Sb–S chain based on the linkage of bow-like [Sb3S7] units and pseudosemicube [In2SbS4] clusters

“…4) were calculated from the reflectance using the Kubelka-Munk function [21]. The weak absorption at 1.27 eV in 1 presumably arises from d-d electronic transition of previously reported molecular Co 2+ complexes [22].The absorption band edge at 2.53 eV could be attributed to the lowest possible electronic excitation located at the [In 2 Sb 4 S 11 4− ] n anion. This value lies in the energy range suitable for visible-light photocatalytic applications [23].…”