Symmetry control of nanorod superlattice driven by a governing force.

Nanoparticle self-assembly promises scalable fabrication of composite materials with unique properties, but symmetry control of assembled structures remains a challenge. By introducing a governing force in the assembly process, we develop a strategy to control assembly symmetry. As a demonstration, we realize the tetragonal superlattice of octagonal gold nanorods, breaking through the only hexagonal symmetry of the superlattice so far. Surprisingly, such sparse tetragonal superstructure exhibits much higher thermostability than its close-packed hexagonal counterpart. Multiscale modeling reveals that the governing force arises from hierarchical molecular and colloidal interactions. This force dominates the interactions involved in the assembly process and determines the superlattice symmetry, leading to the tetragonal superlattice that becomes energetically favorable over its hexagonal counterpart. This strategy might be instructive for designing assembly of various nanoparticles and may open up a new avenue for realizing diverse assembly structures with pre-engineered properties.