Probing Multiscale Factors Affecting the Reactivity of Nanoparticle-Bound Molecules

The structures and physicochemical properties of surface-stabilizing molecules play a critical role in defining the properties, interactions, functionality hybrid nanomaterials such as monolayer-stabilized nanoparticles. Concurrently, distinct surface-bound interfacial environment imposes very specific conditions on molecular reactivity behavior this setting. Our ability to probe nanoscale systems experimentally remains limited, yet understanding consequences surface confinement is crucial for enabling predictive nanoparticle synthon approaches postsynthesis engineering chemistry construction devices materials from components. Here, we have undertaken an integrated experimental computational study reaction kinetics nanoparticle-bound hydrazones, which provide prototypical platform chemical nanoconfined Systematic variation just one molecular-scale structural parameter-the distance between reactive site surface-showed that influenced by multiscale effects. Nanoparticle-bound reactions were tracked situ using 19F NMR spectroscopy, allowing direct comparison analogous substrates bulk solution. surface-confined proceed more slowly than their solution-phase counterparts, kinetic inhibition becomes significant sites positioned closer surface. Molecular dynamics simulations allowed us identify supramolecular architectures unexpected dynamic features underpin observed trends reactivity. This allows draw general conclusions regarding interlinked dynamical across several length scales influence monolayer-confined environments.