Harnessing Secondary Nucleation-Driven Supramolecular Bundled Fibers for Long-Range One-Dimensional Assembly of...

Achieving long-range 1D organization of semiconductor nanocrystals without altering their inherent optical properties is highly challenging, yet crucial for their applications. Herein, we report on the secondary-nucleation-triggered supramolecular polymerization of an alkyl chain-tethered tetraphenylethylene derivative (TPE-A) in dodecane, leading to the formation of ultralong, rigid, bundled and straight 1D fibers. Supramolecular polymerization of TPE-A in dodecane proceeds through a nucleation-elongation mechanism, resulting in non-emissive 1D nanofibers as the primary kinetic aggregates (Aggr_KP). The non-emissive characteristic of Aggr_KP suggests that the tetraphenylethylene (TPE) units within Aggr_KP are in a "monomer-like" state. The TPE units and alkyl chains in Aggr_KP enable their interaction with free monomers in solution, thereby acting as "seed" for catalyzing secondary nucleation. This process leads to the temporal evolution of highly fluorescent, ultralong, rigid bundled fibers as the stable thermodynamic product (Aggr_TP). The enhanced fluorescence of Aggr_TP is attributed to the aggregation-induced emission from the TPE during the bundling of the nanofibers. As a result of secondary-nucleation-triggered bundling, Aggr_TP creates multiple micrometer-long, straight, parallel, 1D hydrophobic lanes. The potential of the hydrophobic lanes in Aggr_TP to serve as a supramolecular template for the long-range 1D organization of semiconductor nanocrystals without compromising their inherent optical properties is demonstrated.