Controlled Polymerization of Norbornene Cycloparaphenylenes Expands Carbon Nanomaterials Design Space

Carbon-based materials-such as graphene nanoribbons, fullerenes, and carbon nanotubes-elicit significant excitement due to their wide-ranging properties and many possible applications. However, the lack of methods for precise synthesis, functionalization, and assembly of complex carbon materials has hindered efforts to define structure-property relationships and develop new carbon materials with unique properties. To overcome this challenge, we employed a combination of bottom-up organic synthesis and controlled polymer synthesis. We designed norbornene-functionalized cycloparaphenylenes (CPPs), a family of macrocycles that map onto armchair carbon nanotubes of varying diameters. Through ring-opening metathesis polymerization, we accessed homopolymers as well as block and statistical copolymers constructed from "carbon nanohoops" with a high degree of structural control. These soluble, sp²-carbon-dense polymers exhibit tunable fluorescence emission and supramolecular responses based on composition and sequence. This work represents an important advance toward bridging the gap between small molecules and functional carbon-based materials.