Post-Synthetic Ligand Exchange by Mechanochemistry: Toward Green, Efficient, and Large-Scale Preparation of Functional Metal-Organic Frameworks

Green, facile, and large-scale preparation of functionalizedmetal-organicframeworks (MOFs) remains a challenge. Herein, we report a rapid synthesisof functionalized MOFs by the integration of post-synthetic ligandexchange (PSLE) and mechanochemistry. This mechano-PSLE approach cancircumvent the hurdles of PSLE such as long reaction time, excessivesolvent, and even failure of PSLE caused by redissolution and recrystallizationunder solvothermal conditions. More importantly, the gram-scale MOFfunctionalized with the chiral group can be obtained facilely andgreenly. It exhibited excellent asymmetric catalytic performance (81%conversion and 92.1% ee) for alpha-alkylation of aldehydes irradiatedby a xenon lamp, providing a basis for industrial batch productionof functionalized MOFs.

Automated summary

We report a rapid synthesis of functionalized metal-organic frameworks (MOFs) by integrating post-synthetic ligand exchange (PSLE) and mechanochemistry. This mechano-PSLE approach overcomes the challenges of PSLE, such as long reaction time, excessive solvent, and PSLE failure under solvothermal conditions. The gram-scale MOF functionalized with a chiral group can be obtained easily and in an environmentally friendly manner. It exhibits excellent asymmetric catalytic performance, providing a basis for the industrial production of functionalized MOFs.