Metal-Organic Frameworks Constructed from Branched Oligomers.

Metal-organic frameworks (MOFs) prepared from oligomeric or polymeric organic ligands have been studied and are termed oligoMOFs and polyMOFs, respectively. Herein, several oligoMOFs are described that have been prepared from branched oligomers with dendritic or star-like architectures. Branched oligomeric ligands with four () or eight () 1,4-benzene dicarboxylic acid (Hbdc) groups were prepared and used to synthesize isoreticular-type Zn(II)-based MOFs (IRMOF). A branched tetramer () produced an oligoIRMOF-1 with improved ambient stability compared with IRMOF-1 or previously described oligoMOFs. To understand the effect of the ligand architecture, oligoIRMOFs were also prepared from a linear tetramer (). For a branched octamer (), it was found that the addition of an organic base was required to produce crystalline oligoIRMOFs. Multivariate MOFs (MTV-MOFs) could also be readily prepared with a combination of an octamer () and Hbdc.