Exfoliation of a Metal-Organic Framework Enabled by Post-Synthetic Cleavage of a Dipyridyl Dianthracene Ligand

The synthetic tunability and porosity of two-dimensional (2D) metal-organic frameworks (MOFs) renders them a promising class of materials for ultrathin and nanoscale applications. Conductive 2D MOFs are of particular interest for applications in nanoelectronics, chemo-sensing, and memory storage. However, the lack of covalency along the stacking axis typically leads to poor crystallinity in 2D MOFs, limiting structural analysis and precluding exfoliation. One strategy to improve crystal growth is to increase order along the stacking direction. Here, we demonstrate the synthesis of mechanically exfoliatable macroscopic crystals of a 2D zinc MOF by selective dimensional reduction of a 3D zinc MOF bearing a dianthracene (diAn) ligand along the stacking axis. The diAn ligand, a thermally cleavable analogue of 4,4’ bipyridine, is synthesized by the direct functionalization of dianthraldehyde in a novel “dianthracene-first” approach. This work presents a new strategy for the growth of macroscopic crystals of 2D materials while introducing the functionalization of dianthraldehyde as a means to access new stimuli-responsive ligands.