Bespoke All-in-one Metallaphotoredox Heterogeneous Catalysts for C-C Cross-Couplings

In synergistic catalysis, multiple catalysts or active sites work together to produce ‘the whole is greater than the sum of its parts’ effect. However, the trilemma of flexibility-stability-cost lies ahead of the multiunit heterogeneous catalyst. As complexity increases, the catalytic efficiency tends to be restricted. Here, we report a general method to tailor modular metallaphotoredox catalysts. The dyes and molecular catalysts could flexibly connect with inexpensive carbon nitride via stable covalent bonds, like LEGO® games. Tunable visible-light absorption, high electron-hole separation efficiency and steerable construction of catalytic active sites have been realized simultaneously, meanwhile the electron transfer mechanism has been clarified via operando techniques. By precisely regulating the coordination field of single-atom sites, four different metallaphotoredox-enabled C-C cross-couplings could be compatible with good cyclic stability (up to 150 hours) and anti-interference ability.