Diversifying Nanoparticle Assemblies in Supramolecule Nanocomposites Via Cylindrical Confinement

Abstract

Many macroscopic properties such as collective chiral responses enhanced by coupled plasmonic nanoparticles require complex nanostructures. However, a key challenge is to directly assemble nanosized building blocks into functional entities with designed morphologies. For example, the DNA templated nanoparticle assembly has low scalability and requires aqueous conditions, while other approaches such as controlled drying and polymer templating access only simple 1-D, 2-D, and 3-D structures with limited assembly patterns. Here, we demonstrate a new self-assembly strategy that expands the diversity of 3-D nanoparticle assemblies. By subjecting supramolecular nanocomposites to cylindrical confinement, a range of new nanoparticle assemblies such as stacked rings and single and double helices can be readily obtained with a precisely defined morphology. Circular dichroism dark field scattering measurements on the single nanowire with Au helical ribbon-like assembly show chiral plasmonic response several orders of magnitude higher than that of natural chiral materials. The phase behavior of supramolecular nanocomposite under geometric constraints is quite different from that of block copolymer. It depends on the complex interplay among nanoparticle packing and phase behavior of parent block copolymers under confinement and can be governed by nanoparticle diffusion. © 2017 American Chemical Society.