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

Abstract

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 sequestrator. Understanding these roles in binary mixtures allows us to rationalize more complex tertiary systems. Consequently, we show here in‐depth the influence of an uncommon dual sequestration mechanism. Further, an unprecedented hybrid mechanism between supramolecular intercalation and sequestration 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.