摘要
The in situ and systematic high-throughput investigation of the system Al 3+ /4,4′-benzophenonedicarboxylic acid (H 2 BPDC)/DMF/H 2 O in the presence of various additives was carried out, and a new Al-MOF of composition [Al(OH)(BPDC)], denoted as CAU-21-BPDC, was obtained. Its crystal structure was determined from single-crystal X-ray diffraction data (space group I422, a = b = 17.2528(7) Å, c = 23.864(1) Å). The structure is built up by octanuclear rings of cis corner-sharing AlO 6 polyhedra forming the inorganic building unit (IBU). These {Al 8 O 8 } IBUs are arranged in a bcu packing and connected via BPDC 2- ions in a way that each IBU is linked via two linker molecules to each of the eight adjacent IBUs. Thus, accessible, one-dimensional modulated pores with a diameter between 3.6 and 6.5 Å are formed. In addition, tetrahedral cavities are formed by the BPDC 2- linker molecules. The framework of CAU-21-BPDC is polymorphous with that of CAU-8-BPDC, which contains one-dimensional chains of trans corner-sharing AlO 6 polyhedra connected by BPDC 2- ions. Replacing H 2 BPDC by 4,4′-oxydibenzoic acid (H 2 ODB), which contains an oxygen atom between the phenyl rings instead of a keto group, leads to the synthesis of Al-MOFs isoreticular with CAU-8-BPDC and CAU-21-BPDC. In addition, a coordination polymer, [Al(HODB) 2 (OH)], was discovered and structurally characterized. The structure of CAU-8-ODB was refined from powder X-ray diffraction data, while a Pawley refinement was carried out for CAU-21-ODB to determine the lattice parameters and confirm phase purity. The structure of CAU-21-ODB was confirmed using density functional theory (DFT) calculations. A thorough characterization shows that the CAU-8 and CAU-21-type structures are stable up to 350 and 300 °C in air, respectively, almost independent of the linker molecules incorporated. The former MOFs are porous toward N 2 and CO 2 , while the latter only adsorb CO 2 .