Self-Organization of Polymer-Tethered Gold Nanoparticles into Hybrid Polyhedral Clusters Confined in Soft Emulsion Droplets

Polymer/inorganic polyhedral clusters organized from polymer-tethered inorganic building blocks have received remarkable attention due to their intriguing crystalline frameworks and functionalities. However, the design of polyhedral clusters remains an enormous challenge, and the sizes are normally restricted to the nanometer scale. Here, we report perfect and large polymer/inorganic hybrid Mackay icosahedral clusters up to the micrometer scale by crystallization of polystyrene-tethered gold inorganic nanoparticles (AuNPs@PS) in soft emulsion droplets. A softness parameter is proposed to evaluate the effect of the softness degree on the shape of the final clusters, which can be utilized to control the framework of supraparticles. Interestingly, a variety of Platonic and Johnson polyhedral clusters with tunable symmetries and configurations have been constructed through manipulating the confinement degree and number of AuNPs@PS building blocks in the confined geometry. The polyhedral clusters in our work open up a universal yet efficient strategy for the bottom-up construction of hybrid polyhedral functional materials.