Chemical and topographic surface patterning of inorganic polymer-functionalized nanoparticles (NPs) and their self-assembly in nanostructures with controllable architectures enable the design of new NP-based materials. Capping of NPs with inorganic polymer ligands, such as metallopolymers, can lead to new synergetic properties of individual NPs or their assemblies, and enhance NP processing in functional materials. Here, for gold NPs functionalized with polyferrocenylsilane, two distinct triggers are used to induce attraction between the polymer ligands and achieve NP self-assembly or topographic surface patterning of individual polymer-capped NPs. Control of polymer-solvent interactions is achieved by either changing the solvent composition or by the electrooxidation of polyferrocenylsilane ligands. These results expand the range of polymer ligands used for NP assembly and patterning, and can be used to explore new self-assembly modalities. The utilization of electrochemical polymer oxidation stimuli at easily accessible potentials broadens the range of stimuli leading to NP self-assembly and patterning.
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