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}
n
(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.