Ma Liqing, Mihalcik David J, Lin Wenbin
Department of Chemistry, CB#3290, University of North Carolina, Chapel Hill, North Carolina 27599, USA.
J Am Chem Soc. 2009 Apr 8;131(13):4610-2. doi: 10.1021/ja809590n.
Highly porous and robust metal-organic frameworks (MOFs) were constructed based on aromatics-rich octa-carboxylate ligands and copper paddle-wheel building units. Each octa-carboxylate ligand is linked to eight copper paddle wheels via the bridging carboxylate groups in a rectangular prismatic fashion to lead to very rare (4,8)-connected networks of the scu topology. The high-connectivity MOFs show remarkably high porosity and framework stability, as evidenced by a perfect agreement between experimental and theoretical surface areas and the maintenance of framework powder X-ray diffraction patterns after solvent removal. These aromatics-rich MOFs exhibit an exceptionally high hydrogen uptake of up to 2.5 wt% at 77 K and 1 atm. This work thus demonstrates the ability to construct highly porous and robust functional MOFs using multidentate bridging ligands of high connectivity. Such a rational synthetic strategy is complementary to the common reliance on high-nuclearity metal clusters for building stable and porous MOFs.
基于富含芳烃的八羧酸配体和铜桨轮构筑单元构建了具有高度多孔性和稳定性的金属有机框架（MOF）。每个八羧酸配体通过桥连羧酸根基团以矩形棱柱的方式与八个铜桨轮相连，形成非常罕见的scu拓扑结构的（4,8）连接网络。高连接性的MOF表现出极高的孔隙率和框架稳定性，实验和理论表面积之间的完美吻合以及溶剂去除后框架粉末X射线衍射图谱的保持证明了这一点。这些富含芳烃的MOF在77 K和1 atm下表现出高达2.5 wt%的异常高的氢吸附量。因此，这项工作展示了使用高连接性的多齿桥连配体构建高度多孔且稳定的功能性MOF的能力。这种合理的合成策略与通常依赖高核金属簇构建稳定且多孔的MOF是互补的。
