Chemically Fueled Amplification of Supramolecular Asymmetry with Double Chiroptical Inversion

Abstract Amplification of asymmetry in supramolecular polymers is typically studied under equilibrium conditions in apolar solvents, while examples in aqueous media, under nonequilibrium conditions or under temporal chemical control remain scarce. Here we demonstrate chemically fueled amplification of supramolecular asymmetry in water using perylene diimide (PDI) derivatives. The chemically fueled reaction cycle uses sodium dithionite to reduce and depolymerize kinetically stable helical aggregates, while subsequent oxidation by dissolved oxygen restores them. This transient disassembly–reassembly process yields amplification of asymmetry in Majority Rules (MR) experiments that is absent in the kinetically trapped system. In Sergeants-and-Soldiers (SaS) experiments, the fueled cycle shows an unusual composition-dependent response characterized by a double chiroptical inversion as a function of sergeant fraction. A phase model captures the emergence of three composition regimes and rationalizes the observed CD response. Overall, we show how chemical fuels can regulate asymmetry amplification in aqueous supramolecular polymers and highlight the role of phase competition in complex chiral self-assembly.