Template-Directed Vertical Photopolymerisation for Construction of Triphenylamine-Based Poly(diacetylene) Nanofibers

Template-directed synthesis of macromolecules prevails in natural systems. However, artificial template-directed covalent polymerisation 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 C 3-symmetric monomers into ordered stacks that evolve from nanodots into micron-scale nanofibers. UV 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. This “self-assemble-then-cure” concept integrates reversible supramolecular organization with irreversible covalent fixation, providing a general route to vertically oriented conjugated materials. The dual control of alignment and bond formation demonstrates a scalable strategy for designing responsive polymeric architectures, bridging supramolecular precision with robust covalent frameworks.