Photoredox Heterobimetallic Dual Catalysis Using Engineered Covalent Organic Frameworks.

The functionalization of an imine-based layered covalent organic framework (COF), containing phenanthroline units as ligands, has allowed the obtention of a heterobimetallated material. Photoactive Ir and Ni fragments were immobilized within the porous structure of the COF, enabling heterogeneous light-mediated Csp 3 -Csp 2 cross-couplings. As radical precursors, potassium benzyl- and alkoxy-trifluoroborates, organic silicates, and proline derivatives were employed, which brings out the good versatility of Ir,Ni@Phen-COF . Moreover, in all the studied cases, an enhanced activity and stability have been observed in comparison with analogous homogenous systems.