Controlled Polymerization of Norbornene Cycloparaphenylenes Expands Carbon Nanomaterials Design Space

[Image: see text] 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, sp(2)-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.