Multipolar Donor‐Acceptor Conjugated Hypercrosslinked Polymers for Enhanced Visible‐Light Photoreduction of CO ₂ to CO

Multipolar donor‐acceptor (D‐A) hypercrosslinked polymers provide well‐defined charge–transfer pathways that enable efficient and selective CO 2 photoreduction under visible light. While such systems hold promise for CO 2 conversion, achieving high activity, long‐term stability, and product selectivity remains challenging. Here, we present HCP‐CoTPP‐Cz‐1, a multipolar D‐A hypercrosslinked conjugated polymer synthesized via Scholl coupling. HCP‐CoTPP‐Cz‐1 exhibits a high CO 2 adsorption capacity of 9.71 wt% at 273 K, which is associated with cobalt‐containing units incorporated within the polymer network. In addition, the extended π‐conjugated D‐A framework promotes efficient charge separation and charge‐carrier transport. Under photocatalytic conditions employing [Ru(bpy) 3 ]Cl 2 as the photosensitizer and triethanolamine as the hole‐sacrificial agent, HCP‐CoTPP‐Cz‐1 achieves a CO evolution rate of 4402.5 µmol g −1 h −1 with an apparent quantum yield of 0.51% at 450 nm, representing a 37.5% enhancement compared with the non‐D‐A polymer HCP‐CoTPP‐s. Both catalysts maintain CO selectivity >99%. Mechanistic studies reveal that the multipolar D–A architecture facilitates charge separation and transfer, suppresses electron–hole recombination, and enhances both CO 2 capture capacity and catalytic stability. By demonstrating a rational polymer design that enables efficient and stable CO 2 photoreduction, this work presents a feasible strategy to convert CO 2 into CO within green chemical production pathways.