Atomically Precise Integration of Ruthenium–Terpyridine Chromophores Into Covalent–Organic Frameworks Affords Exfoliable Platforms for Synergistic Photocatalytic CO 2 Reduction

Developing an efficient photocatalytic system for CO 2 reduction is a sustainable strategy for producing value‐added products. However, conversion efficiency is significantly limited by ineffective coordination among light harvesting, excited‐state dynamics, and interfacial electron transfer. Herein, we report a binary photocatalytic system for CO 2 reduction by integrating an exfoliable Ru‐integrated covalent–organic framework (COF–Ru–TPY) with a molecular cocatalyst ([M(bpy) 3 ] 2+ ). Compared with the non‐metalated COF, this atom‐level‐precise integration strategy not only broadens visible light absorption and narrows the optical band gap but also prolongs the excited‐state lifetime. Notably, the COF–Ru–TPY/[Zn(bpy) 3 ] 2+ achieves a competitive CO production rate of 1.01 mmol g −1 h −1 and > 99% CO selectivity, comparing favorably with representative COF‐based photocatalytic systems. Combined experimental characterizations and theoretical calculations indicate that precisely anchoring Ru(TPY) 2 chromophores improved the optical response and excited‐state behavior of the COF. Calculations suggested a lower work function. The Ru‐integrated framework provides a more polarized electronic environment that is beneficial for charge redistribution. This work highlights that atom‐level‐precise anchoring of molecular chromophores is an effective strategy for constructing COF‐based binary photocatalytic systems with improved excited‐state utilization and interfacial charge transfer.