Non-Noble Metal Anchored 2D Covalent Organic Framework for Ambient CO₂ Fixation to High-Value Compounds

The catalytic functionalization of CO₂ into high-value compounds comprises a promising approach to mitigate its atmospheric content and sustainable generation of fine chemicals. In this respect, covalent organic frameworks (COFs) offer great potential in carbon dioxide capture and utilization. Herein, we report application of a crystalline, nanoporous 2D COF (ET-BP-COF) obtained by condensation of 4,4',4'',4'''-(ethene-1,1,2,2-tetrayl) tetraaniline (ET-NH₂) and 2,2'-bipyridyl-5,5'-dialdehyde (BP-CHO) building blocks for strategic utilization of CO₂. The ET-BP-COF features a unique 2D kagome (kgm) topology composed of hexagonal and triangular 1D channels decorated with bipyridine sites, which were exploited for covalent anchoring of eco-friendly, alkynophilic Cu(I) by the post-synthetic method. The Cu(I) engrafted COF was applied as a recyclable catalyst for coupling CO₂ with alkynes to generate two high-value compounds, α-alkylidene cyclic carbonates (α-ACCs) and 2-oxazolidinones. Notably, Cu(I)@ET-BP-COF demonstrated excellent catalytic performance for transforming propargylic amine and CO₂ to 2-oxazolidinone, an essential building block for antibiotics. Besides, an efficient transformation of propargylic alcohols to generate α-ACCs, valuable commodity chemicals, has been achieved by utilizing carbon dioxide. Further, detailed theoretical simulations disclosed the insight mechanistic path of Cu(I) catalyzed coupling of CO₂ and alkynes to produce 2-oxazolidinones and α-ACCs. Significantly, the Cu(I)@COF was reusable for multiple cycles without losing framework rigidity and catalytic performance. This study showcases the potential application of ET-BP-COF for stable anchoring of eco-friendly metals as catalytic sites for effective utilization of CO₂ to produce two high-value products, 2-oxazolidinones and α-ACCs, under mild atmospheric conditions.