Photoredox Heterobimetallic Dual Catalysis Using Engineered Covalent Organic Frameworks

Area of Science:

• Materials Science
• Organic Chemistry
• Catalysis

Background:

• Covalent organic frameworks (COFs) offer tunable porous structures for catalyst immobilization.
• Imine-based COFs provide versatile platforms for incorporating functional units.
• Heterogeneous catalysis is crucial for sustainable chemical synthesis.

Purpose of the Study:

• To develop a heterobimetallated COF for enhanced catalytic performance.
• To investigate the use of photoactive iridium (Ir) and nickel (Ni) fragments within a COF.
• To explore the COF's efficacy in light-mediated Csp³-Csp² cross-coupling reactions.

Main Methods:

• Functionalization of an imine-based COF with phenanthroline ligands.
• Immobilization of photoactive Ir and Ni fragments within the COF structure, creating Ir,Ni@Phen-COF.
• Utilizing various radical precursors like trifluoroborates, organic silicates, and proline derivatives.

Main Results:

• Successful synthesis of a heterobimetallated Ir,Ni@Phen-COF material.
• Demonstrated efficient heterogeneous light-mediated Csp³-Csp² cross-coupling reactions.
• Observed enhanced catalytic activity and stability compared to homogeneous counterparts.

Conclusions:

• The developed Ir,Ni@Phen-COF is a versatile and stable heterogeneous catalyst.
• This approach enables efficient light-mediated cross-coupling with broad substrate scope.
• Heterogenization of catalytic fragments within COFs presents a promising strategy for advanced catalysis.