| This thesis explores a range of powerful -- and oftentimes exotic -- chemical properties that emerge when molecules are confined to nanoscopic dimensions. After an overview of various supramolecular designs that enable nanoscale confinement, the remainder of the thesis will highlight this author's unique contributions to the field.;Specifically, self-assembled monolayers of organic molecules on gold nanoparticles can serve as an environment that enforces co-localization of a catalyst and reactants. The result is a new type of supramolecular environment that enhances catalytic reactivity. This environment is composed of a Cu(I) species coordinated within the monolayer and surrounded by inert alkyl chains, and greatly prefers the inclusion of ionic molecules over neutral molecules. This preference for charged molecules in chemical reactions was found to be as high as a factor of 30.;This same catalytic environment is also employed to probe cooperativity in catalysis. Since the composition of the monolayer on the nanoparticle can be varied, it is possible to 'dilute' one component of the monolayer with respect to the other. As a consequence, the average distance between these components can be precisely controlled. Here, this strategy is employed to show the first definitive evidence that two copper atoms participate in the catalytic cycle of the Cu(I)-catalyzed azide/alkyne cycloaddition.;Monolayers can also mediate the assembly -- reversible and irreversible -- of the surfaces to which they're attached. Here, assemblies of both spherical nanoparticles and nanotriangles rely crucially on such monolayers to provide the driving force that guides them into the desired positions. For spherical nanoparticle assemblies, monolayers drive aggregation and precipitation that form the basis for an irreversible temperature sensor that 'records' whether a sample was brought above a certain temperature, TM . This same aggregation phenomenon can be precisely controlled to grow 300 nm 'supraspheres' composed of individual nanoparticles, whose plastic deformation at the nanoscale can be effected by macroscopic stresses and shears. In the case of nanotriangles, surfactant monolayers provide an electrostatic means to assemble superlattices spanning hundreds of mum 2. Lastly, electrostatic repulsion between surfactant molecules leads to macroscopic droplet division, partitioning nanoscale 'cargo' into discrete micellar containers. |
