Symmetry-Broken Patches on Gold Nanoparticles through Deficient Ligand Exchange

Symmetry-broken nanoparticles (NPs) are important building blocks with directional interparticle interaction as a key to access the precise organization of NPs macroscopically. We report a facile, one-pot synthetic approach to prepare high-quality symmetry-broken plasmonic gold NPs (AuNPs). Symmetry-broken patterning is achieved through deficient ligand exchange of isotropic AuNPs with thiol-terminated polystyrene (PS-SH) in the presence of an amphiphilic polymer surfactant. The concentration of PS-SH plays a dominant role in tuning surface patterning and coverage of AuNPs. The formation of asymmetric surface patches arises from the interplay between the conformational entropy of polymer ligands and the interfacial energy between polymer-grafted AuNPs and the solvent. Our method illustrates new paradises to design asymmetric NPs with directional interparticle interactions to access the precise organization of NPs.