Diverse chiral assemblies of nanoparticles directed by achiral block copolymers <i>via</i> nanochannel confinement

Abstract

It is a challenging task to realize large-area manufacture of chiral geometries of nanoparticles in solid-state materials, which exhibit strongly chiroptical responses in the visible and near-infrared ranges. Herein, novel nanocomposites, made from mixtures of achiral block copolymers and nanoparticles in a geometrically confined environment, are conceptually proposed to construct the chiral assemblies of nanoparticles through a joint theoretical-calculation framework and experimental discussion. It is found that the nanochannel-confined block copolymers self-assemble into a family of intrinsically chiral architectures, which serve as structural scaffolds to direct the chiral arrangement of nanoparticles. Through calculations of chiral order parameters and simulations of discrete dipole approximation, it is further demonstrated that certain members of this family of nanoparticle assemblies exhibit intense chiroptical activity, which can be tailored by the nanochannel radius and the nanoparticle loading. These findings highlight the multiple levels of structural control over a class of chiral assemblies of nanoparticles and the functionalities of emerging materials via careful design and selection of nanocomposites.