Designing Atomically Precise and Robust COF Hybrids for Efficient Photocatalytic CO₂ Reduction

Abstract Hybrid photocatalysts based on molecular species and solid substrates are elegant solutions for improving the performance and stability of molecular catalytic systems aiming at solar‐driven CO 2 conversion. In this work, a new dibenzochrysene‐based covalent organic framework (COF) is developed to accept Re I centers, keeping its high crystallinity and allowing for atomistic control of the position of the catalytic centers. The rigid structure of the COF leads to long‐term stability under illumination, whereas the efficient light‐harvesting capability and the strong electronic interactions between the COF and the Re I centers lead to CO evolution rates of up to 1.16 mmol g −1 h −1 . The favorable photocatalytic performance of this novel Re I ‐COF offers new insights regarding the development of efficient photocatalytic hybrid systems.