Template-directed vertical photopolymerization for construction of triphenylamine-based poly(diacetylene) nanofibers

Template-directed synthesis of macromolecules prevails in natural systems. However, artificial template-directed covalent polymerization that proceeds without sacrificing the delicate non-covalent order needed for precursor alignment remains a formidable challenge. Here we report a supramolecular-templating strategy for photopolymerization of triphenylamine-based diyne assemblies. Cooperative hydrogen- and halogen-bonding align C₃-symmetric monomers into ordered stacks that evolve from nanodots into micron-scale nanofibers. Ultraviolet irradiation then triggers axial cross-linking of the diyne moieties, producing continuous one-dimensional conjugated polymers. Selective acid treatment cleaves the I···N halogen bond to remove the template while preserving nanofibrillar integrity, yielding a stable covalent network with red-shifted emission. We demonstrate that this self-assemble-then-cure strategy integrates reversible supramolecular organization with irreversible covalent fixation, providing a general and scalable route to vertically oriented conjugated polymer architectures.