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Inspired by biology, in which a bimetallic hydroxide-bridged zinc(II)-containing enzyme is utilized to catalytically hydrolyze phosphate ester bonds, the utility of a zirconium(IV)-cluster-containing metal-organic framework as a catalyst for the methanolysis and hydrolysis of phosphate-based nerve agent simulants was examined. The combination of the strong Lewis-acidic Zr(IV) and bridging hydroxide anions led to ultrafast half-lives for these solvolysis reactions. This is especially remarkable considering that the actual catalyst loading was a mere 0.045 % as a result of the surface-only catalysis observed.

Metal-organic frameworks (MOFs) have gained considerable attention as hybrid materials-in part because of a multitude of potential useful applications, ranging from gas separation to catalysis and light harvesting. Unfortunately, de novo synthesis of MOFs with desirable function-property combinations is not always reliable and may suffer from vagaries such as formation of undesirable topologies, low solubility of precursors, and loss of functionality of the sensitive network components. The recently discovered synthetic approach coined solvent-assisted linker exchange (SALE) constitutes a simple to implement strategy for circumventing these setbacks; its use has already led to the generation of a variety of MOF materials previously unobtainable by direct synthesis methods. This Review provides a perspective of the achievements in MOF research that have been made possible with SALE and examines the studies that have facilitated the understanding and broadened the scope of use of this invaluable synthetic tool.