Dynamic covalent chemistry steers synchronizing nanoparticle self-assembly with interfacial polymerization

Precise organization of matter across multiple length scales is of particular interest because of its great potential with advanced functions and properties. Here we demonstrate a simple yet versatile strategy that enables the organization of hydrophobic nanoparticles within the covalent organic framework (COF) in an emulsion droplet. The interfacial polymerization takes place upon the addition of Lewis acid in the aqueous phase, which allows the formation of COF after a crystallization process. Meanwhile, the interaction between nanoparticles and COF is realized by the use of amine-aldehyde reactions in the nearest loci of the nanoparticles. Importantly, the competition between the nanoparticle self-assembly and interfacial polymerization allows control over the spatial distribution of nanoparticles within COF. As a general strategy, a wide variety of COF-wrapped nanoparticle assemblies can be synthesized and these hybridized nanomaterials could find applications in optoelectronics, heterogeneous catalysis and energy chemistry.