Photoresponsive Palladium and Nickel Catalysts for Ethylene Polymerization and Copolymerization

In this contribution, we install an azobenzene functionality in olefin polymerization catalysts and use light to modulate their properties via photoinduced trans – cis isomerization of the azobenzene moiety. The initially targeted azobenzene‐functionalized α‐diimine palladium and nickel catalysts are not photoresponsive. To address this issue, an imine–amine system bearing interrupted conjugation with the metal center, and a sandwich‐type α‐diimine system bearing an azobenzene unit at a position covalently far from the metal center were prepared and studied. We demonstrate that light can be used to tune their properties in ethylene polymerization and copolymerization with polar comonomers, enabling light‐induced control of the polymerization processes, polymer microstructures and polymer properties. More interestingly, the light‐mediated property changes were attributed to ligand electronic effects in one system and ligand steric effects in the other.