Polyoxometalate-Based AgI-MOF for Promoting Catalytic Conversion of CO2 and Propargylic Alcohols under Mild Conditions.

The conversion of carbon dioxide to high-value chemicals is greatly significant to green chemistry. The cyclization reaction of CO2 with propargyl alcohol to form α-alkylidene cyclic carbonates has attracted attention due to atomic economy. Silver (AgI) has emerged as one of the most effective activators for alkynes, attributed to its distinctive electronic configuration affording a specific affinity with alkynes. Herein, two novel AgI-based metal-organic frameworks containing Keggin PMo12O403- (abbreviated as {PMo12}), namely, {Ag3(btap)3[PMo12O40]}·H2O (Ag-1) and {Ag(Hbtap)2[PMo12O40]} (Ag-2, btap is 3,5-bis(1',2',4'-triazol-1'-yl)pyridine), were successfully synthesized. Ag-1 exhibits both exceptional thermal and solvent stability, along with high catalytic activity in CO2 cyclization with various substituted propargylic alcohols into α-alkyl cyclic carbonates at room temperature and atmospheric pressure. The highly dispersed AgI and {PMo12} sites are beneficial for the superior performance of Ag-1, by activating the C≡C bond and adsorbing carbon dioxide, respectively. Based on the catalytic results, structural analysis, and classical chemical bond theory, it is speculated that the three-coordinated silver in Ag-1 has higher Lewis acidity compared with Ag-2, making it easier to activate the substrate. Notably, the Ag-1 catalyst exhibits outstanding stability with negligible activity loss over at least five successive cycles.