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The idea to synthesize and self-assemble nano-graphenes with structural precision into supramolecular polymers is just one of Klaus Müllen's many pioneering contributions to the chemical sciences. To honor his impact in the field of polymer science, we here describe a study that combines experimental and computational methods in studying the stability of kinetically trapped states of supramolecular polymers. We show that the introduction of stereocenters in the sidechains allow helical supramolecular polymers based on chiral triphenylene-2,6,10-tricarboxamide monomers to escape a kinetic trap more efficiently than polymers based on their achiral analogs. Partial depolymerization of the kinetically trapped state by increasing the temperature followed by polymerization by lowering the temperature shows that monomers either polymerize on existing stacks or self-nucleate to form the thermodynamically more stable state. Chiral monomers prefer the latter more than achiral monomers.

The desire to construct complex molecular systems is driven by the need for technological (r)evolution and our intrinsic curiosity to comprehend the origin of life. Supramolecular chemists tackle this challenge by combining covalent and noncovalent reactions leading to multicomponent systems with emerging complexity. However, this synthetic strategy often coincides with difficult preparation protocols and a narrow window of suitable conditions. Here, we report on unsuspected observations of our group that highlight the impact of subtle “irregularities” on supramolecular systems. Based on the effects of pathway complexity, minute amounts of water in organic solvents or small impurities in the supramolecular building block, we discuss potential pitfalls in the study of complex systems. This article is intended to draw attention to often overlooked details and to initiate an open discussion on the importance of reporting experimental details to increase reproducibility in supramolecular chemistry.

Recent investigations of supramolecular polymers based on chiral triphenylene-2,6,10-tricarboxamides (TTAs) showed how temperature-induced changes in solvation can greatly influence the preferred helical conformation of the supramolecular polymers formed. Here, we combine chiral TTA with achiral copolymerization partners to further investigate temperature-dependent solvation effects. Systematic variation of the system's composition shows clear impacts on the temperature window where the conformational change occurs. Further, simple chain length variations in the achiral comonomer greatly affect the ability to influence the conformational change in the copolymer, while the differences in the properties of the individual homopolymers are rather small. We herein highlight how subtle changes in the monomers can impact the observed copolymer properties drastically; an effect arising from the emerging complexity of multicomponent interactions in supramolecular copolymers with solvent-solute interactions being more important than typically thought.