Development of Solvent-Dispersible Coordination Polymer Nanocrystals and Application as Efficient Heterogeneous Catalysts

Abstract

Nonporous coordination polymers (CPs) constructed from flexible bridging ligands have seldom been utilized in practical applications, owing to limited solubility and/or stability in most solvents. Here we have produced nanocrystal coordination polymers (NCPs) with identical crystalline structure to their macroscale counterparts, high solvent dispersibility, and large effective surface area for catalytic application. A microemulsion system has been developed for the mild synthesis of the ZnII- and CuII-NCPs, resulting in control over the size, morphology, and reactivity. Both ZnII- and CuII-NCPs demonstrated high catalytic activity in a ring opening reaction of cyclohexene oxide with aniline; furthermore, reduced Cu-NCPs were employed as efficient, reusable catalysts for an azide–alkyne cycloaddition “click” reaction in the nonpolar solvent heptane. In contrast, all macroscale CP equivalents, prepared by conventional methods, were catalytically inactive.