CO₂ coordination-driven top-down synthesis of a 2D non-layered metal-organic framework

Combining the physical advantages of two-dimensional (2D) inorganic nanosheets and the modular design and programmed structure of metal-organic frameworks (MOFs), 2D MOFs remain at the forefront of functional material research. Despite tremendous efforts, precise control in the synthesis of 2D nonlayered MOFs with predesigned topology for desired applications remains challenging. Success in the bottom-up synthesis of 2D nonlayered MOFs via ligand exchange motivated us to incorporate partial BTC (BTC = 1,3,5-benzenetricarboxylate) ligand dissociation and CO₂ capped coordination into the top-down treatment of bulk Cu-BTC MOF, leading to successful conversion of a 3D nonlayered network to a 2D Cu-based topological structure. Notably, a supercritical CO₂-containing solvent mixture is employed to provide the desired defect and coordination engineering. Thus, our work introduces a new top-down concept based on modulated synthesis to fabricate high-quality 2D nonlayered MOFs for the first time.