Cooperativity is a central design principle developed by Nature to trigger and regulate specific biological processes. In enzymes, the underlying thermodynamic and kinetic basis behind cooperativity relies generally on complex multiscale mechanisms comprising confinement, preorganization, selective binding or allosteric regulation. These concepts have often served as a major source of inspiration for the design of artificial catalytic systems, which primarily requires being able to orchestrate with precision the network of molecular interactions essential for cooperativity.<br/> <br/>Herein, we present a general method for the simultaneous co-immobilization of multiple molecular catalysts on mesoporous silica surfaces. The method allows precisely controlling and modulating the relative composition and intersite interactions in a supported trifunctional catalytic system comprising Cu, TEMPO and NMI active centers intended towards the selective aerobic oxidation of alcohols. Following molecular engineering of the mixed monolayer, it is possible to significantly enhance reaction rates compared to the free, disordered, system as a result of preorganized synergistic interactions within the confined pores of the silica support. Likewise, we demonstrate that a higher level of precision can be achieved by directing the distribution and positioning of the three active centers beyond their statistical arrangement in mixed monolayers using precision oligomer scaffolds. Combining sequence information together with oriented surface grafting and dense confinement hence uncovers a new paradigm towards the rational precision design of multifunctional active sites, relying on the tailoring of the probabilities of synergistic interactions.

Molecular engineering of multifunctional monolayers for the cooperative aerobic oxidation of alcohols

256th National Meeting (2018)

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