Tuning the Activity-Stability Balance of Photocatalytic Organic Materials for Oxidative Coupling Reactions

Three materials containing a photoactive unit, 10-phenyl phenothiazine (PTH), have been studied for the visible light-mediated oxidative coupling of amines. In particular, the materials considered are assembled through the condensation of extended polyimine, polyhydrazone, or polytriazine frameworks. These three materials present different stabilities in the presence of strong nucleophiles such as amines, which is a key factor for efficient catalytic performance. In the series of materials reported herein, the triazine-based material shows the optimal compromise between activity and stability when studied for the oxidative coupling of amines, achieving imine products. Accordingly, while significant leaching of molecular active fragments is ruled out for triazine-based polymers, other materials of the series show a significant chemical erosion as a result of the reaction with the amine substrates. Consequently, only a triazine-based material allows performing several catalytic cycles (up to seven) with yields higher than 80%. The applicability of this heterogeneous catalyst has been proven with a variety of substrates, confirming its stability and obtaining diverse imine coupling products with excellent yields.