Pyrene-Containing Polymer-Supported Cu/TEMPO Catalytic Systems: Aromatic Stacking-Enhanced Cooperative Catalysis

Noncovalent immobilization of discrete molecular species on polymer supports is a unique approach to engineer multifunctional cooperative catalysts. Here we devise a modular strategy for the construction of polymer-supported Cu/2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) catalytic systems by using hydrophobic interactions and aromatic stacking interactions. Polymer-supported Cu/TEMPO catalysts prepared by nanoprecipitation exhibit excellent catalytic activities for aerobic oxidation of benzyl alcohol, which can be tailored by the type of aromatic moieties, effective constituent ratios, and polymer compositions. We found that strong aromatic stacking interactions and the use of pyrene-containing polymers are crucial to enhance cooperativity. This modular strategy is promising for the immobilization of multifunctional cooperative catalysts with excellent catalytic activities and has potential for the engineering of other heterogeneous multifunctional catalysts.