Fluorescent Hybrid Porous Polymers as Sustainable Heterogeneous Photocatalysts for Cross-Dehydrogenative Coupling Reactions

A series of hybrid porous polymers (HPPs) based on polyhedral oligomeric silsesquioxane (POSS) were synthesized, characterized, and successfully used as metal-free heterogeneous photocatalysts for cross-dehydrogenative coupling reactions (CDC), for which the aza-Henry coupling of tetrahydroisoquinolines and nitroalkanes was studied as the model reaction. The reactions run smoothly at room temperature under visible (blue) light irradiation using gaseous oxygen as an oxidant under atmospheric pressure. These novel metal-free heterogeneous photocatalysts can be readily recovered and reused without a significant loss of reactivity. Mechanistic investigations revealed the intermediacy of 1O2, obtained from 3O2 sensitization (energy transfer) by the photoexcited catalyst.