Harnessing Naphthalimide Scaffolds for Sustainable CO ₂ Utilization: A Metal‐, Halide‐, and Solvent‐Free Photocatalytic CO ₂ Cycloaddition via Sequential Two‐Photon Activation

Consecutive photoinduced electron transfer (ConPET) has attracted great interest due to its ability to activate inert substrates under mild reaction conditions. The imide‐functionalized rylene derivatives are well‐documented in the literature as competent chromophores capable of operating via ConPET. Herein, we report the synthesis and characterization of naphthalimide‐based organophotocatalyst, JS‐2, for CO 2 cycloaddition with epoxides to synthesize cyclic carbonates. JS‐2 demonstrated remarkable efficiency with just 0.1 mol% catalyst loading at room temperature, atmospheric CO 2 pressure, and under visible light irradiation, giving excellent yield and selectivity for a wide range of substrates. Detailed mechanistic investigations and density functional theory calculations confirmed that the reaction proceeds via a sequential two‐photon excitation, forming the CO 2 radical anion (CO 2 •− ) as a nucleophile. The heterogeneity and excellent recyclability across five consecutive cycles highlight the robustness and feasibility of the catalyst for practical use. To the best of our knowledge, this is the first report of a completely metal‐, halide‐, and solvent‐free approach, employing a ConPET process and leveraging the nucleophilic reactivity of CO 2 •− in epoxide ring opening for a photocatalytic CO 2 cycloaddition reaction.