Unusual CD-ee Dependence in Self-Assembled Chiral Nanocomposites through Nanoparticle-Mediated Interactions

Supramolecular self-assembly can produce a linear or a positive nonlinear CD versus enantiomeric excess (ee) relationship. Negative “racemate rules” behavior is rare. In this work, we report an unusual nonlinear CD-ee dependence in a coassembly system comprising chiral perylene diimide molecules and gold nanoparticles (AuNPs). In contrast to the linear majority-rules behavior observed for pure PDI molecules, the introduction of AuNPs induces a tendency toward heterochiral coaggregation, leading to a negative CD-ee correlation at low temperature (278 K) and a positive correlation at high temperature (318 K). Even both positive and negative CD-ee correlations can coexist and be tuned within a single self-assembling system. Combined molecular dynamics simulations and preassembly control experiments demonstrate that the nanoparticles reshape the chiral recognition pathway of PDI molecules through alkyl chain–chain van der Waals interactions, while the assembly temperature further modulates the majority-rules behavior. This work reveals a mechanism by which nanoparticles act as regulatory units in supramolecular chirality, offering a design strategy for programmable chiral materials.