Precision Colloidal Polymerization of Hierarchical Gold Nanocluster Assemblies

The precisely directed self-assembly of nanomaterials into highly ordered hierarchical nanostructure assemblies exhibits interesting synergistic and coupling effects. However, the precision-directed construction of hierarchical nanoparticle assemblies possessing controlled morphology and properties is a contemporary challenge owing to the uncontrollable building unit nanoparticles. Herein, a polymer unimolecular micelle-guided self-assembly strategy was used to fabricate highly ordered hierarchical atomically precise gold nanocluster (AuNC) assemblies with rationally designed star-like diblock copolymers as patched polymer templates. Nearly monodispersed spherical secondary structural nanocluster assemblies with well-defined interaction anisotropies on surface patches were prepared as colloidal monomers, which could manipulate the precision colloidal polymerization of these nanoparticles with different symmetries into larger hierarchical complex morphologies (1D chain, branch, sphere) in different solvent mixtures. The investigation of the kinetics allowed quantitative control of the degree of polymerization for linear hierarchical nanocluster chains. Thus, we deduce that this star-like polymer unimolecular micelle template-guided self-assembly strategy may provide a facile and powerful platform for the fabrication of hierarchical nanomaterial aggregates for potential applications such as catalysis, optics, bioimaging, etc.