Li H, Laine A, O'Keeffe M, Yaghi OM
Supramolecular Design and Discovery Group, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85287, USA.
Science. 1999 Feb 19;283(5405):1145-7. doi: 10.1126/science.283.5405.1145.
Although aluminosilicates and metal phosphates can form porous open-framework materials such as zeolites, sulfide analogs usually form high-density phases because of the relatively small tetrahedral angle at sulfur atoms. One strategy to overcome this limitation is to use tetrahedral clusters as the building blocks to achieve porous sulfide-based networks. The preparation and crystal structures of two indium sulfide open frameworks (ASU-31 and ASU-32) built of supertetrahedral clusters around organic template and water guests are described. ASU-31, based on the sodalite-tetrahedrite network, contains cavities 25.6 angstroms in diameter, and ASU-32, based on the tetragonal CrB4 network, contains channels with a minimum diameter of 14.7 angstroms. The organic cations can be completely exchanged with sodium ions in aqueous solution at room temperature without degradation of the crystals.
尽管铝硅酸盐和金属磷酸盐能够形成诸如沸石之类的多孔开放框架材料，但硫化物类似物通常会形成高密度相，这是因为硫原子处的四面体角相对较小。克服这一限制的一种策略是使用四面体簇作为构建单元，以实现基于硫化物的多孔网络。本文描述了两种围绕有机模板和水客体由超四面体簇构建而成的硫化铟开放框架（ASU - 31和ASU - 32）的制备方法及其晶体结构。基于方钠石 - 黝铜矿网络的ASU - 31含有直径为25.6埃的空腔，而基于四方CrB4网络的ASU - 32含有最小直径为14.7埃的通道。在室温下，有机阳离子可在水溶液中与钠离子完全交换，而晶体不会降解。
