A Hafnium-Based Metal–Organic Framework as an Efficient and Multifunctional Catalyst for Facile CO₂ Fixation and Regioselective and Enantioretentive Epoxide Activation

Porous heterogeneous catalysts play a pivotal role in the chemical industry. Herein a new Hf-based metal-organic framework (Hf-NU-1000) incorporating Hf6 clusters is reported. It demonstrates high catalytic efficiency for the activation of epoxides, facilitating the quantitative chemical fixation of CO2 into five-membered cyclic carbonates under ambient conditions, rendering this material an excellent catalyst. As a multifunctional catalyst, Hf-NU-1000 is also efficient for other epoxide activations, leading to the regioselective and enantioretentive formation of 1,2-bifuctionalized systems via solvolytic nucleophilic ring opening.