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 [Cu(CO)(HO)] clusters and meticulously designed fluorine-funtionalized tetratopic 2',3'-difluoro-[-terphenyl]-3,3″,5,5″-tetracarboxylic acid (F-Hptta) engenders one peculiar nanocaged {Cu}-organic framework of {[Cu(F-ptta)(HO)]·5DMF·2HO} (), 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 [Cu(COO)HO)] 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 exhibits excellent catalytic performance on the cycloaddition reaction of CO 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 . Also, 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.

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http://dx.doi.org/10.1021/acs.inorgchem.2c01686DOI Listing

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