Synthetic Polymers To Promote Cooperative Cu Activity for O2 Activation: Poly vs Mono.

We report polymer-promoted cooperative catalysis of Cu for oxygen activation. A series of random copolymers containing dipicolylamine as binding motifs are designed to coordinate type-3 Cu sites. The Cu-copolymers show a 6-8-fold activity enhancement, compared to the molecular complex of Cu with an identical coordination site. Michaelis-Menten analysis demonstrates that the kinetic enhancement results from flexible polymer-promoted cooperative catalysis among multi-Cu sites despite the imposed thermodynamic barrier. These observations provide guidance for the bioinspired design of metallopolymers as soluble catalysts with high activity.