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

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

A Robust Sulfonate-Based Metal–Organic Framework with Permanent Porosity for Efficient CO₂ Capture and Conversion

We report a rare example of a sulfonate-based metal–organic framework (MOF) possessing a prototypical primitive-cubic topology, constructed with Jahn–Teller distorted Cu­(II) centers and a mixed-linker (organosulfonate and N-donor) system. The inherent highly polar, permanent porosity contributes to the highest reported CO₂ sorption properties to date among organosulfonate-based MOFs, outperforming the benchmark carboxylate MOF counterpart. Importantly, density functional theory calculations confirm that the CO₂–sulfonate interaction plays an important role in CO₂ capture. Indeed, the hydrothermal product demonstrates high robustness over a wide pH range as well as aqueous boiling conditions, overcoming the moisture sensitivity of conventional Cu₂ paddlewheel-based MOFs. In addition, bulk synthesis of this material has been successfully achieved on a gram scale (>1 g) in a single batch with a high yield. Combining the high CO₂ affinity and a robust nature, this sulfonate porous material is also an efficient, recyclable heterogeneous catalyst for CO₂ fixation to form cyclic carbonates under ambient conditions

A Robust Sulfonate-Based Metal–Organic Framework with Permanent Porosity for Efficient CO₂ Capture and Conversion

We report a rare example of a sulfonate-based metal–organic framework (MOF) possessing a prototypical primitive-cubic topology, constructed with Jahn–Teller distorted Cu­(II) centers and a mixed-linker (organosulfonate and N-donor) system. The inherent highly polar, permanent porosity contributes to the highest reported CO₂ sorption properties to date among organosulfonate-based MOFs, outperforming the benchmark carboxylate MOF counterpart. Importantly, density functional theory calculations confirm that the CO₂–sulfonate interaction plays an important role in CO₂ capture. Indeed, the hydrothermal product demonstrates high robustness over a wide pH range as well as aqueous boiling conditions, overcoming the moisture sensitivity of conventional Cu₂ paddlewheel-based MOFs. In addition, bulk synthesis of this material has been successfully achieved on a gram scale (>1 g) in a single batch with a high yield. Combining the high CO₂ affinity and a robust nature, this sulfonate porous material is also an efficient, recyclable heterogeneous catalyst for CO₂ fixation to form cyclic carbonates under ambient conditions