Icosahedral supracrystal assembly from polymer-grafted nanoparticles via interplay of interfacial energy and confinement effect.

Self-assembly of nanoparticles (NPs) in drying emulsion droplets paves the way for intricate three-dimensional (3D) superstructures, given the myriad of control parameters for fine-tuning assembly conditions. With their substantial energetic dynamics that are acutely responsive to emulsion confinements, polymeric ligands incorporated into a system can enrich its structural diversity. Here, we demonstrate the assembly of soft polymer-grafted NPs into Mackay icosahedrons beyond spherical body-centered cubic (BCC) packing structures commonly observed for these soft spheres. This behavior is governed by the free energy minimization within emulsions through the interplay of the oil-water interfacial energy and confinement effect as demonstrated by the experimental observations of structural transitions between icosahedrons and BCC crystals and by corresponding free energy calculations. The anisotropic surface of the icosahedral supracrystals provides the capability of guiding the position of a secondary constituent, creating unique hybrid patchy icosahedrons with the potential to develop into multifunctional 3D clusters that combine the benefits of both polymers and conventional colloids.