Reimer Nele, Reinsch Helge, Inge A Ken, Stock Norbert
Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel , Max-Eyth-Strasse 2, D-24118 Kiel, Germany.
Inorg Chem. 2015 Jan 20;54(2):492-501. doi: 10.1021/ic502242j. Epub 2014 Dec 24.
A new sulfone-functionalized metal-organic framework [Al(OH)(SDBA)]·0.25DMF, denoted CAU-11, was synthesized using a V-shaped linker molecule 4,4'-sulfonyldibenzoic acid (H2SDBA). The crystal structure was solved from synchrotron X-ray powder diffraction data. Chains of trans corner-sharing AlO6 octahedra are interconnected by the carboxylate groups to form layers (ABAB stacking). Within the layers, hydrophobic lozenge-shaped pores with a diameter of 6.4 × 7.1 Å(2) are present inducing permanent porosity (aBET = 350 m(2) g(-1) and Vmicro = 0.17 cm(3) g(-1)). With the application of HT-methods (HT = high throughput), the isoreticular carboxylate functionalized compound [Al(OH)(H2DPSTC)]·0.5H2O (CAU-11-COOH) was synthesized using the linker molecule 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DPSDA), which hydrolyzes under the reaction conditions. Due to the additional noncoordinating carboxylic acid groups the pores are hydrophilic. Changing the molar ratio of Al(3+) to linker lead to the discovery of a second new compound [Al2(OH)2(DPSTC)(H2O)2]·0.5H2O (CAU-12). In CAU-12 the linker molecule is fully deprotonated which leads to different connectivity compared to the structure of CAU-11-COOH. Thermal activation of CAU-12 leads to dehydration and transformation of the structure to [Al2(OH)2(DPSTC)]·nH2O (CAU-12-dehy). Coordinated water molecules were removed, and the coordination site is replaced by the previously noncoordinating O atom of the adjacent carboxylate group. The SO2-groups point into the pores resulting in a highly hydrophobic three-dimensional framework. The compounds exhibit high thermal stability in air at least up to 420 °C. Synthesis of CAU-11 can be easily scaled up in very high yields (98%).
使用V形连接分子4,4'-磺酰基二苯甲酸（H2SDBA）合成了一种新的砜官能化金属有机框架[Al(OH)(SDBA)]·0.25DMF，记为CAU-11。晶体结构由同步加速器X射线粉末衍射数据解析得出。反式角共享AlO6八面体链通过羧酸根基团相互连接形成层（ABAB堆积）。在层内，存在直径为6.4×7.1 Å(2)的疏水性菱形孔，导致其具有永久孔隙率（aBET = 350 m(2) g(-1)，Vmicro = 0.17 cm(3) g(-1)）。通过高通量方法（HT = high throughput），使用连接分子3,3',4,4'-二苯基砜四羧酸二酐（DPSDA）合成了等规羧酸官能化化合物[Al(OH)(H2DPSTC)]·0.5H2O（CAU-11-COOH），该连接分子在反应条件下会水解。由于额外的非配位羧酸基团，孔具有亲水性。改变Al(3+)与连接分子的摩尔比导致发现了第二种新化合物[Al2(OH)2(DPSTC)(H2O)2]·0.5H2O（CAU-12）。在CAU-12中，连接分子完全去质子化，这导致其与CAU-11-COOH的结构相比具有不同的连接性。CAU-12的热活化导致脱水并将结构转变为[Al2(OH)2(DPSTC)]·nH2O（CAU-12-dehy）。配位水分子被去除，配位位点被相邻羧酸根基团先前的非配位O原子取代。SO2基团指向孔内，形成高度疏水的三维框架。这些化合物在空气中至少在420°C时表现出高的热稳定性。CAU-11的合成可以很容易地以非常高的产率（98%）放大规模。
