Colloidal Cluster Assembly into Ordered Superstructures via Engineered Directional Binding.

Recent experimental studies have demonstrated a facile route for fabricating large numbers of geometrically uniform colloidal clusters out of submicron DNA-functionalized spheres. These clusters are ideally suited for use as anisotropic building blocks for hierarchical assembly of superstructures with symmetries that are otherwise inaccessible with simple spherical particles. We study computationally the self-assembly of cubic, tetrahedral, and octahedral clusters mediated by "bond spheres" that dock with the clusters at specific preferential sites, providing robust and well-defined directional bonding. We analyze the assembly process with a combination of direct molecular dynamics simulations of superstructure growth and state-of-the-art umbrella sampling techniques to compute nucleation free energy profiles. The simulations confirm the versatility and robustness of hierarchical cluster assembly but also reveal potential obstacles in the form of energetically accessible defect states. We find and study solutions for bypassing these defects that rely on appropriate selection of particle size and interparticle interaction as a function of building block shape and, therefore, provide operational guidelines for future experimental demonstrations.