DirectionalSelf-Assembly of Programmable Atom-likeNanoparticles into Colloidal Molecules

Colloidal molecules, novel nanoparticle clusters with molecular-like structures, can enhance material performance and broaden applications in nanotechnology and materials science. However, constructing them with a precise, controllable architecture remains challenging. Inspired by the concepts of chemical reaction, we theoretically design a novel type of nanoparticles bifunctionalized by DNA strands and polymer chains and propose a stepwise strategy to hierarchically program the assembly of bifunctionalized nanoparticles into well-defined colloidal molecules by virtue of coarse-grained molecular dynamics simulations. This method leverages the synergistic effects of polymers and DNA to create programmable atom-like nanoparticles with various valence domains. By carefully designing strands, these nanoparticles are programmed to coassemble into various colloidal molecules with distinct symmetries and coordination numbers, which can be finely tuned by the molecular design of nanoparticles as well as the composition design of the coassembly system. Our strategy provides a novel protocol for the controlled coassembly of nanoparticles into customized colloidal molecules, expanding nanomaterial manufacturing techniques.