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

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 CO₂ 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.