4.8 Article

Photoredox Heterobimetallic Dual Catalysis Using Engineered Covalent Organic Frameworks

Journal

ACS CATALYSIS
Volume 11, Issue 19, Pages 12344-12354

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c03634

Keywords

covalent organic frameworks; photocatalysis; dual catalysis; C-C bond formation; heterogeneous catalysis

Funding

  1. European Research Council (ERC-CoG) [647550]
  2. Spanish Government [RTI2018-095038-B-I00, PID2019-110637RBI00]
  3. Comunidad de Madrid
  4. European Structural Funds [S2018/NMT-4367]
  5. UAM for FPIUAM predoctoral fellowship
  6. Spanish MINECO [SEV-2017-0706]

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The functionalization of an imine-based layered covalent organic framework has allowed the obtention of a heterobimetallated material with photoactive Ir and Ni fragments immobilized within the porous structure. These heterogeneous light-mediated reactions showed enhanced activity and stability compared to analogous homogeneous systems.
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.

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