Coordination bond cleavage and controlled reconstruction in MOFs: strategic post-synthetic modification for targeted applications

Metal-organic frameworks (MOFs) have enormous potential for catalysis, gas separation, and gas storage, owing to their porous, crystalline nature. Nevertheless, conventional synthesis methods tend to yield the so-called perfect topologies, which exhibit extremely poor diffusion and limited access to the inner active sites and thus cannot meet the demands of specific applications. To overcome these intrinsic bottlenecks, post-synthetic modification (PSM) has become an important regulatory tool. Cleavage of Coordination Bond and Reconstruction is a revolutionary “top-down” paradigm for molecular surgery. This review offers a detailed overview of the methods for directing the disassembly and restructuring of MOFs in response to various stimuli: chemical changes (acid or alkaline reactions, salt hydrolysis, ligand exchange), thermal pyrolysis, and physical/radiative excitation. This strategy precisely manipulates hierarchical porosities, reveals active sites, and controls chemical composition without random framework disintegration, by treating the lability of coordination bonds as a programmable characteristic rather than a structural defect. Moreover, we provide an outline of how this controlled structural evolution leads to high-performance derivatives, such as amorphous MOFs, metal/carbon nanostructures, and 2D nanosheets. The exceptional structure-property relationships of these rebuilt structures are emphasized in high-end uses, including fire retardancy, adsorption/separation, efficient electrocatalysis, and emerging frontiers such as sustainable anticorrosion. Finally, this review links the most fundamental molecular scission dynamics to macroscopic functions, providing a generic plan for the rational development of task-oriented MOF derivatives.