Chiral Self-Assembly of Nanoparticles Induced by Polymers Synthesized via Reversible Addition-Fragmentation Chain Transfer Polymerization.

Chiral inorganic nanomaterials are of great interest because of their excellent optical properties. Most of the attention has been focused on the utilization of biomolecules or their derivatives as linkers or templates to control the chiral structure of assembled inorganic nanoparticles. Chiral polymers are promising synthetic materials that can be used to replace their biological counterparts. Here, by using poly(methacrylate hydroxyethyl-3-indole propionate) (PIPEMA) and poly(2-hydroxyethyl methacrylate) (PHEMA) synthesized via syndioselective reversible addition-fragmentation chain transfer polymerization, we successfully realized chiral self-assembly of gold nanorods with strong circular dichroism response in the vis-NIR region. Moreover, the intensity of the chiral signal of the assemblies can be regulated by the molecular weight of the polymers. Notably, although the monomers are achiral and no chiral reagents are involved in their synthesis, the main chains of PIPEMA and PHEMA exhibit a preferred-handed helical conformation, which is the origin of chirality of the nanorod assemblies. The preferred-handed helical conformation of polymers is attributed to their syndiotacticity and stabilized by the steric hindrance of the side groups. The addition of chiral carbon atoms at the side groups does not change the preferred-handedness of the polymer main chain, resulting in the assembled nanorod structures with the same chirality. This strategy provides inspiration for the rational design and synthesis of optically active functional synthetic polymers for the preparation of promising chiral nanomaterials.