Interaction‐Specific Control Over Self‐Assembly Landscape and Supramolecular Chirality

Supramolecular chirality in molecular assemblies is often an outcome of cooperative interactions that can result from multiple short- and long-range noncovalent interactions operating in tandem. The ability to manipulate a single interaction out of a collection of noncovalent interactions can arguably affect cooperativity and thus alter supramolecular chirality. We present such an interaction-specific control over supramolecular chirality in the aqueous self-assembly of a pair of enantiomeric perylene bisimides. Each enantiomer assembles into three distinct chiral states, including a pair of mirror-image structures. These can be accessed either by specific heating/cooling protocols or by varying the water-cosolvent ratio. An unprecedented control over this complex self-assembly landscape is achieved by selectively and reversibly turning off the carboxylic acid-mediated hydrogen-bonding interaction, such that the assembly can be guided toward any specific chiral state in a deterministic fashion. The generality of our strategy is demonstrated by carrying out similar supramolecular stereomutation for structurally related molecules.