Rapid, Precise, and Robust Supramolecular Polymerization from Functional Oligomeric‐Charged Poly(3‐hexylthiophene) Amphiphiles

Abstract Nature inspires the design of artificial systems with remarkable rapidity, precision, and functionality, yet achieving these attributes simultaneously remains a challenge. Living crystallization‐driven self‐assembly (CDSA) methods have enabled the formation of low‐dispersity block copolymer nanofibers with crystalline cores, but these processes typically involve moderate or slow growth kinetics to ensure well‐controlled and ordered epitaxial crystallization. Here, we report studies on the living CDSA of oligomeric‐charged poly(3‐hexylthiophene) amphiphiles, demonstrating an unprecedented combination of rapidity and precision. We show that self‐seeding can produce nanofibers with controllable lengths up to ∼700 nm within ∼15 min (including 5 min of disassembly and 10 min of re‐growth), while seeded growth can generate nanofibers up to > 2000 nm in length within ∼20–40 min, depending on the unimer‐to‐seed mass ratios. Notably, this robust supramolecular polymerization can be initiated from the surfaces of two‐dimensional nanosheets, resulting in hierarchical hairy structures grafted with dense, uniform micellar brushes.