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<p>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 <i>C</i><sub><i>3</i></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.</p>

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

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年2月28日

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  • Yingbo Lu,
  • Luyao Jin,
  • Jiani Wang,
  • Qiang Fang,
  • Shuping Wang,
  • Jianying Huang,
  • Zibin Zhang,
  • Feihe Huang,
  • Shijun Li

摘要

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.