Nanoporous {Y}-Organic Frameworks for Excellent Catalytic Performance on the Cycloaddition Reaction of Epoxides with CO and Deacetalization-Knoevenagel Condensation.

Stable metal-organic frameworks containing periodically arranged nanosized pores and active Lewis acid-base active sites are considered as ideal candidates for efficient heterogeneous catalysis. Herein, the exquisite combination of [Y(CO)(HO)] cluster (abbreviated as {Y}) and multifunctional linker of 2,4,6-tri(2,4-dicarboxyphenyl)pyridine (HTDP) led to a nanoporous framework of {[Y(TDP)(HO)]·5HO·4DMF} (, NUC = North University of China), which is a rarely reported binuclear three-dimensional (3D) framework with hierarchical tetragonal-microporous (0.78 nm) and octagonal-nanoporous (1.75 nm) channels. The inner walls of these channels are aligned by {Y} clusters and plentifully coexisted Lewis acid-base sites of Y ions and N atoms. Furthermore, has a quite large void volume of ∼65.2%, which is significantly higher than most documented 3D rare-earth-based MOFs. The performed catalytic experiments exhibited that activated showed a high catalytic activity on the cycloaddition reactions of CO with styrene oxide under mild conditions with excellent turnover number (TON: 1980) and turnover frequency (TOF: 495 h). Moreover, the deacetalization-Knoevenagel condensation reactions of benzaldehyde dimethyl acetal and malononitrile could be efficiently prompted by the heterogeneous catalyst of . These findings not only pave the way for the construction of nanoporous MOF based on rare-earth clusters with a variety of catalytic activities but also provide some new insights into the catalytic mechanism.