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

Lu, Yingbo; Jin, Luyao; Wang, Jiani; Fang, Qiang; Wang, Shuping; Huang, Jianying; Zhang, Zibin; Huang, Feihe et al. · Nat Commun · 2026

basic_science · Level V

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Abstract

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 C<sub>3</sub>-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.