Additive-induced kinetic control and chiral amplification in circularly polarized luminescence (CPL)-emitting secondary supramolecular polymers.

Seeded supramolecular polymerization (SSP) has emerged as a powerful strategy for achieving precise size and shape control in supramolecular architectures through kinetic regulation of nucleation and growth processes. However, precise modulation of spontaneous nucleation events through predictable pathway complexity remains challenging. Arresting active monomers using non-integrating additives to modulate supramolecular polymerization pathways is still largely underexplored. Particularly, nucleation-controlled tunability of excited-state chiroptical luminescent properties in supramolecular polymers via external additives remains elusive. Herein, we demonstrate additive-induced controlled supramolecular polymerization, establishing a direct link between seed-catalyzed secondary nucleation and excited-state circularly polarized luminescence (CPL). An amide-functionalized chiral naphthalene monoimide (NMI-1) undergoes self-assembly via uncontrolled nucleation-elongation in decane, forming stable hydrogen-bonded CPL-emitting nanorods temporally. To suppress this pathway, an electron-deficient naphthalene diimide (NDI-1) additive is introduced, which sequesters NMI-1 through aromatic interactions into kinetically stable, CPL-silent spherical aggregates, effectively trapping the monomer in a dormant state for a prolonged period. Upon seeding, trapped NMI-1 released via decomplexation undergoes seed-catalyzed secondary nucleation from the CPL-emitting nanorods, while the excluded NDI-1 forms self-sorted structures. This additive-mediated controlled nucleation enables chiral amplification in the hierarchical assembly of NMI-1 in the excited state, leading to a ten-fold increment in the g lum value, relative to the self-nucleated SP.