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

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.