Elucidating the Boundary of Intercalation vs. Sequestration in Supramolecular Polymers by Retrosynthetic Design Towards the Construction of Complex Supramolecular Systems

Controlled social self-sorting by intercalation can offer distinct properties at the supramolecular level that go beyond the sum of its parts. Likewise, controlling narcissistic self-sorting by sequestration can induce unique system properties such as dilution-induced self-assembly. In contrast, the interface between the two extreme cases has hitherto remained underexplored and clear design rules remain elusive. Herein we demonstrate that by fine-tuning the molecular similarity of supramolecular synthons in a complex system, intricate control over concerted supramolecular equilibria can be achieved. By reducing the molecular similarity, a former intercalator can be tuned to become a strong or weak sequestrators. As a consequence, either uncommon dual supramolecular sequestration or an unprecedented competitive hybrid mechanism between sequestration and intercalation in tertiary mixtures could be demonstrated. We are hopeful that the results presented herein will contribute to the development and understanding of concerted processes in complex supramolecular systems.