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

Abstract 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.