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Green and rational synthesis of porous MOFs and their non-conventional forms via mechanochemistry

Porous metal-organic frameworks (MOFs)[1] have become a highly researched area of modern materials science. MOFs are modular coordination materials whose structure and properties can be altered by a careful choice of metal nodes and suitable organic linkers. They are now widely studied for storage, separation, catalysis, sensing, light-harvesting, and other applications. [2] Microporous MOFs are now commercialized, but the standard synthetic procedures, involving an excess of organic solvents and harsh reaction conditions, still prevent their wider industrial application. Here we present how mechanochemical reactions, [3], i.e. reactions between solid reactants induced by mechanical force, can be used for a rapid, sustainable, and controllable transformation of environmentally safe precursors into relevant microporous MOFs, such as MOF-74[4] or zirconium- based MOFs of UiO[5], NU-[6], and PCN-[7] families. It is particularly suitable for the preparation of their multi-metal or amorphous derivatives by using only a catalytic amount of green liquids, such as alcohols or water. Direct monitoring by powder X-ray diffraction [8] revealed that the mechanochemical formation of MOFs often proceeds through intermediate phases, most of which are inaccessible from solution procedures. It is possible to isolate and characterize these intermediates and use them for the controllable synthesis of non-conventional MOFs, such as various bimetallic MOF-74 materials, [9] with interesting magnetic properties and strong potential for new catalytic reactivity.

Mechanochemistry ; coordination compounds polymorphism ; organic synthesis

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