A “Shake ‘n Bake Route” to Functionalised Zr-UiO-66 Metal-Organic Frameworks

We report a novel synthetic procedure for the high-yield synthesis of metal-organic frameworks with UiO-66 topology starting from a range of commercial ZrIV precursors and various substituted dicarboxylic linkers. The syntheses are carried out by grinding in a ball mill the starting reagents, namely Zr salts and the dicarboxylic linkers, in the presence of a small amount of acetic acid and water (1 mL total volume for 1 mmol of each reagent), followed by incubation at either room temperature or 120 °C. Such a “shake ‘n bake” procedure avoids the use of large amounts of solvents generally used for the syntheses of Zr-MOF. Acidity of the linkers and the amount of water are found to be crucial factors in affording materials of quality comparable to that of products obtained in solvo- or hydrothermal conditions.