Cluster-based MOFs with accelerated chemical conversion of CO₂ through C-C bond formation

Investigations on metal-organic frameworks (MOFs) as direct catalysts have been well documented, but direct catalysis of the chemical conversion of terminal alkynes and CO₂ as chemical feedstock by MOFs into valuable chemical products has never been reported. We report here two cluster-based MOFs I and II assembled from a multinuclear Gd-cluster and Cu-cluster, displaying high thermal and solvent stabilities. I and II as heterogeneous catalysts possess active catalytic centers [Cu₁₂I₁₂] and [Cu₃I₂], respectively, exhibiting excellent catalytic performance in the carboxylation reactions of CO₂ with 14 kinds of terminal alkynes under 1 atm and mild conditions. For the first time catalysis of the carboxylation reaction of terminal alkynes with CO₂ by MOF materials without any cocatalyst/additive is reported. This work not only reduces greenhouse gas emission but also provides highly valuable materials, opening a wide space in seeking recoverable catalysts to accelerate the chemical conversion of CO₂.