Fluorine-Functionalized NbO-Type {Cu₂}-Organic Framework: Enhanced Catalytic Performance on the Cycloaddition...

The high catalytic activity of metal-organic frameworks (MOFs) can be realized by increasing their effective active sites, which prompts us to perform the functionalization on selected linkers by introducing a strong Lewis basic group of fluorine. Herein, the exquisite combination of paddle-wheel [Cu₂(CO₂)₄(H₂O)] clusters and meticulously designed fluorine-funtionalized tetratopic 2',3'-difluoro-[p-terphenyl]-3,3″,5,5″-tetracarboxylic acid (F-H₄ptta) engenders one peculiar nanocaged {Cu₂}-organic framework of {[Cu₂(F-ptta)(H₂O)₂]·5DMF·2H₂O} (NUC-54), which features two types of nanocaged voids (9.8 Å × 17.2 Å and 10.1 Å × 12.4 Å) shaped by 12 paddle-wheel [Cu₂(COO)₄H₂O)₂] secondary building units, leaving a calculated solvent-accessible void volume of 60.6%. Because of the introduction of plentifully Lewis base sites of fluorine groups, activated NUC-54a exhibits excellent catalytic performance on the cycloaddition reaction of CO₂ with various epoxides under mild conditions. Moreover, to expand the catalytic scope, the deacetalization-Knoevenagel condensation reactions of benzaldehyde dimethyl acetal and malononitrile were performed using the heterogenous catalyst of NUC-54a. Also, NUC-54a features high recyclability and catalytic stability with excellent catalytic performance in subsequent catalytic tests. Therefore, this work not only puts forward a new solution for developing high-efficiency heterogeneous catalysts, but also enriches the functionalization strategies for nanoporous MOFs.