Unusual Missing Linkers in an Organosulfonate-Based Primitive–Cubic (pcu)-Type Metal–Organic Framework for CO₂ Capture and Conversion under Ambient Conditions

A noninterpenetrated organosulfonate-based metal–organic framework (MOF) with a defective primitive–cubic (pcu) topology was successfully synthesized. The unusual missing linkers, along with the highest permanent porosity (∼43%) in sulfonate-MOFs, offer a versatile platform for the incorporation of alkynophilic Ag(I) sites. The cyclic carboxylation of alkyne molecules (e.g., propargyl alcohol and propargyl amine) into α-alkylidene cyclic carbonates and oxazolidinones were successfully catalyzed by the use of Ag(I)-embedded sulfonate-MOF under atmospheric pressure of CO2. In all the three catalytic reactions using CO2 as a C1 feedstock, the highly robust sulfonate-based MOF catalyst exhibit at least three-cycle reusability.