Temperature Directs the Majority‐Rules Principle in Supramolecular Copolymers Driven by Triazine–Benzene Interactions

Abstract

AbstractSupramolecular copolymers have typically been studied in the extreme cases, such as self‐sorting or highly mixed copolymer systems, while the intermediate systems have been less understood. We have reported the temperature‐dependent microstructure in copolymers of triazine‐ and benzene‐derivatives based on charge‐transfer interactions with a highly alternating microstructure at low temperatures. Here, we investigate the temperature‐dependent copolymerization further and increase the complexity by combining triazine‐ and benzene‐derivatives with opposite preferred helicities. In this case, intercalation of the benzene‐derivative into the triazine‐derivative assemblies causes a helical inversion. The inversion of the net helicity was rationalized by comparing the mismatch penalties of the individual monomers, which indicated that the benzene‐derivative dictates the helical screw‐sense of the supramolecular copolymers. Surprisingly, this was not reflected in further investigations of slightly modified triazine‐ and benzene‐derivatives, thus highlighting that the outcome is a subtle balance between structural features, where small differences can be amplified due to the competitive nature of the interactions. Overall, these findings suggest that the temperature‐dependent microstructure of triazine‐ and benzene‐based supramolecular copolymers determines the copolymer helicity of the presented system in a similar way as the mixed majority‐rules phenomenon.