Architecting Stable Silver-Based MOF for Conversion of Propargylic Amines and Propargylic Alcohols with CO₂ under...

The utilization of CO₂ to prepare value-added chemicals has been considered as a promising project because it can not only mitigate CO₂ emissions but also provide important chemicals. Herein, an Ag-MOF {[Ag₄O(Tipe)₃](NO₃)₂}_n (Tipe = 1, 1, 2, 2-tetrakis(4-(1H-imidazole-4-yl)phenyl)ethylene) was synthesized and exhibits a 3D and 4, 12-connected {4³⁶·6³⁰}{4⁴·6²}₃ topological network with a tetrahedral Ag₄O cluster. Ag-MOF has thermal and solvent stability and exceptional light stability. Additionally, Ag-MOF shows highly catalytic activity toward the conversion of CO₂ into oxazolidinone from propargylic amines under mild conditions (1 atm CO₂, rt), which achieves moderate to excellent yields and has good substrate adaptability and recycling ability. Moreover, Ag-MOF can also be employed for catalyzing the cycloaddition of CO₂ and propargylic alcohols to yield α-alkylidene cyclic carbonate under mild conditions (1 atm CO₂, rt), achieving moderate to excellent yields and a certain recyclability. Moreover, gram-scale experiments were conducted with excellent yields. Significantly, the transformation of flue gas (15 vol % CO₂) to oxazolidinones using propargylic amines affords good to excellent yields. Experiments reveal that the synergetic activation of the substrate by Ag-MOF and base facilitates the reaction process, highlighting the practical application of MOFs for catalytically dual transformation of CO₂.