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<p>Understanding how molecules in solution begin to nucleate and grow into defined aggregates remains an outstanding mechanistic challenge. This is because the nucleation process is affected by a number of physicochemical factors that act simultaneously and whose individual contributions are hard to disentangle. Here, we demonstrate how residual aggregates in a molecular dispersion state affect the nucleation kinetics and the resulting self-assembly pathway. Using the photoisomerization of a chiral azobenzene molecule, the amounts of residual aggregates can be controlled in the pre-assembly supersaturated solution. The residual aggregates induce surface-catalysed secondary nucleation of monomers, affecting the chiral intermolecular configuration during self-assembly to afford metastable right-handed <i>P</i>-aggregates as opposed to thermodynamically stable left-handed <i>M</i>-aggregates. By exploiting the photoisomerization process, we establish high-fidelity control over the nucleation processes and demonstrate reversible <i>M</i> ⇄ off ⇄ <i>P</i> tristate switching of supramolecular chirality. Finally, we show that chiral aggregates exhibit opposite chirality-induced spin selectivities with high spin-polarization rates.</p>

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Inversion of supramolecular chirality by photo-enhanced secondary nucleation

  • 期刊论文

  • 发表日期：

    2025年4月11日

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  • Takuho Saito,
  • Daisuke Inoue,
  • Yuichi Kitamoto,
  • Hiroki Hanayama,
  • Takatoshi Fujita,
  • Yuki Watanabe,
  • Masayuki Suda,
  • Takashi Hirose,
  • Takashi Kajitani,
  • Shiki Yagai

摘要

Understanding how molecules in solution begin to nucleate and grow into defined aggregates remains an outstanding mechanistic challenge. This is because the nucleation process is affected by a number of physicochemical factors that act simultaneously and whose individual contributions are hard to disentangle. Here, we demonstrate how residual aggregates in a molecular dispersion state affect the nucleation kinetics and the resulting self-assembly pathway. Using the photoisomerization of a chiral azobenzene molecule, the amounts of residual aggregates can be controlled in the pre-assembly supersaturated solution. The residual aggregates induce surface-catalysed secondary nucleation of monomers, affecting the chiral intermolecular configuration during self-assembly to afford metastable right-handed P-aggregates as opposed to thermodynamically stable left-handed M-aggregates. By exploiting the photoisomerization process, we establish high-fidelity control over the nucleation processes and demonstrate reversible M ⇄ off ⇄ P tristate switching of supramolecular chirality. Finally, we show that chiral aggregates exhibit opposite chirality-induced spin selectivities with high spin-polarization rates.