The role of dynamic metal-ligand bonds in metal-organic framework chemistry

Metal-organic frameworks (MOFs) are an emerging class of porous materials composed of metal ions or clusters interconnected by organic ligands. Many proposed applications for MOFs take advantage of the modular design, porosity, and crystallinity of these materials. However, the rigid lattice portrayed by crystallography betrays the dynamic nature of the underlying metal–ligand coordination bonds. The reversibility of coordination chemistry is critical for the emergence of crystallinity in extended metal–organic lattices, but it also underpins framework decomposition processes and emerging functionality. It is evident that our understanding of MOFs has continued to evolve as the role of dynamic properties is increasingly understood and exploited. This is perhaps most evident in the recent appearance of liquid and glass MOF phases. This review explores the role of dynamic metal-linker interactions in pertinent examples of MOF chemistry, including lattice formation, catalysis, adsorption, and framework modulation.