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<p>Chiral supramolecular polymerization enables precise construction of helical nanostructures, yet the stereochemical hierarchy governing helicity in multichiral systems remains poorly understood. Although conventional enantiomeric systems primarily follow ‘majority-rule’ principles due to equivalent homopolymerization energetics, here we engineer two α-cyanostilbene positional isomers with intentionally mismatched homopolymerization energy landscapes. Stereocentre repositioning induces divergent assembly behaviours: the first isomer exclusively forms <i>P</i>-helical polymers, whereas the second exhibits two competing pathways with opposite <i>M</i>/<i>P</i>-helical conformations. Strikingly, supramolecular copolymerization reveals ‘helicity-overriding’ behaviour—the minimal first isomer (&lt;20 mol%) overrides the thermodynamically favoured <i>M</i>-helical state of the second isomer, enforcing uniform <i>P</i>-helicity under both thermodynamic and kinetic conditions. Mechanistic studies identify cooperative <i>π</i>–<i>π</i> stacking and hydrogen-bonding interactions as key drivers stabilizing <i>P</i>-helical conformations in supramolecular copolymers. This work establishes an energy landscape engineering approach for helicity programming in supramolecular polymers, offering insights into asymmetry amplification in multicomponent systems and advancing the rational design of adaptive chiral nanomaterials.</p><p></p>

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Energy landscape modulation enables helicity overriding in supramolecular copolymers

  • 期刊论文

  • 发表日期：

    2025年9月19日

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  • Yuncong Xue,
  • Yu Huang,
  • Siwei Chen,
  • Jianfei Ma,
  • Shiyan Xiao,
  • Feng Wang

摘要

Chiral supramolecular polymerization enables precise construction of helical nanostructures, yet the stereochemical hierarchy governing helicity in multichiral systems remains poorly understood. Although conventional enantiomeric systems primarily follow ‘majority-rule’ principles due to equivalent homopolymerization energetics, here we engineer two α-cyanostilbene positional isomers with intentionally mismatched homopolymerization energy landscapes. Stereocentre repositioning induces divergent assembly behaviours: the first isomer exclusively forms P-helical polymers, whereas the second exhibits two competing pathways with opposite M/P-helical conformations. Strikingly, supramolecular copolymerization reveals ‘helicity-overriding’ behaviour—the minimal first isomer (<20 mol%) overrides the thermodynamically favoured M-helical state of the second isomer, enforcing uniform P-helicity under both thermodynamic and kinetic conditions. Mechanistic studies identify cooperative π–π stacking and hydrogen-bonding interactions as key drivers stabilizing P-helical conformations in supramolecular copolymers. This work establishes an energy landscape engineering approach for helicity programming in supramolecular polymers, offering insights into asymmetry amplification in multicomponent systems and advancing the rational design of adaptive chiral nanomaterials.