Photoredox Heterobimetallic Dual Catalysis Using Engineered Covalent Organic Frameworks
Abstract
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-Cspcross-couplings. As radical precursors, potassium benzyl- and alkoxy-trifluoroborates, organic silicates, and proline derivatives were employed, which brings out the good versatility ofIr,Ni@Phen-COF. Moreover, in all the studied cases, an enhanced activity and stability have been observed in comparison with analogous homogenous systems. ; Financial support was provided by the European Research Council (ERC-CoG, contract no. 647550), the Spanish Government (RTI2018-095038-B-I00, PID2019-110637RB-I00), "Comunidad de Madrid", and European Structural Funds (S2018/NMT-4367). A.L.M. thanks to UAM for FPI-UAM predoctoral fellowship. ICN2 is supported by the Severo Ochoa programme from the Spanish MINECO (Grant No. SEV-2017-0706).
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