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<p>Templated polymerization within confined spaces offers a powerful route to tailor polymer structures and properties, yet structural details of confined polymers at the atomic level remain obscure owing to challenges in obtaining high-quality single crystals. Here we report the single-crystal X-ray structures of helical polythiophene and polypyrrole, produced by in situ radical polymerization of achiral monomers in a chiral metal–organic framework (MOF) featuring redox-active tri-iron(III) clusters. Crystallographic analysis reveals that both polymers adopt single-handed helical conformations, stabilized by supramolecular interactions with pore surfaces. Unexpectedly, the helical chains grow through narrow catalytic channels rather than in wide pores, as previously assumed. The confined helicity substantially amplifies the chirality-induced spin selectivity of the MOF, yielding spin polarization of up to 94% and demonstrating the key role of helicity in spin selectivity. Our work lays the foundation for the rational design of single-crystalline porous hybrids with tunable electronic, optical and quantum properties that surpass conventional crystals.</p><p></p>

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Helical polymer metal–organic framework hybrids

  • 期刊论文

  • 发表日期：

    2025年10月21日

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  • Xinfa Chen,
  • Xiaofeng Zhang,
  • Can Leng,
  • Chao Jiang,
  • Wei Gong,
  • Yan Liu,
  • Yong Cui

摘要

Templated polymerization within confined spaces offers a powerful route to tailor polymer structures and properties, yet structural details of confined polymers at the atomic level remain obscure owing to challenges in obtaining high-quality single crystals. Here we report the single-crystal X-ray structures of helical polythiophene and polypyrrole, produced by in situ radical polymerization of achiral monomers in a chiral metal–organic framework (MOF) featuring redox-active tri-iron(III) clusters. Crystallographic analysis reveals that both polymers adopt single-handed helical conformations, stabilized by supramolecular interactions with pore surfaces. Unexpectedly, the helical chains grow through narrow catalytic channels rather than in wide pores, as previously assumed. The confined helicity substantially amplifies the chirality-induced spin selectivity of the MOF, yielding spin polarization of up to 94% and demonstrating the key role of helicity in spin selectivity. Our work lays the foundation for the rational design of single-crystalline porous hybrids with tunable electronic, optical and quantum properties that surpass conventional crystals.