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<p>Ring-opening metathesis polymerization (ROMP) of strained cycloalkenes, driven by angle strain relief, has emerged as a powerful and versatile approach for synthesizing macromolecular materials. Nevertheless, the ROMP of C=C bonds upon stretching remains unexplored. Here, we employ a molecular-strain engineering approach by incorporating stretched C=C bonds into bowstrings of molecular bows (MBs) with different tension levels. This approach enables us to investigate the ROMP of the C=C bonds under varying tensile forces. Remarkably, increased tensile force applied to the <i>cis</i>-C=C bond leads to significant deceleration of the ROMP reaction, whereas the <i>trans</i>-isomer exhibits a pronounced acceleration under the same conditions. This contrasting response was theoretically established to originate from the differential strain-induced modulation of the activation energy. Critically, applied tensile force thus governs directly both the kinetics and mechanistic pathway of ROMP, selectively promoting cyclic oligomer formation and establishing a molecular-strain-engineering paradigm that transcends conventional ring-strain-driven polymerization.</p>

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Stretching decelerates ring-opening metathesis at cis-olefins in stressed molecular bows

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2026年7月22日

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  • Liang Jiang,
  • Guoao Li,
  • Jiali Liu,
  • Yu Wang,
  • Jingqi Chen,
  • Zheng-Bin Tang,
  • Kejiang Liang,
  • Jin Yin,
  • Zhen Peng,
  • Wenjie Dou,
  • Shuhua Li,
  • Zhichang Liu

摘要

Ring-opening metathesis polymerization (ROMP) of strained cycloalkenes, driven by angle strain relief, has emerged as a powerful and versatile approach for synthesizing macromolecular materials. Nevertheless, the ROMP of C=C bonds upon stretching remains unexplored. Here, we employ a molecular-strain engineering approach by incorporating stretched C=C bonds into bowstrings of molecular bows (MBs) with different tension levels. This approach enables us to investigate the ROMP of the C=C bonds under varying tensile forces. Remarkably, increased tensile force applied to the cis-C=C bond leads to significant deceleration of the ROMP reaction, whereas the trans-isomer exhibits a pronounced acceleration under the same conditions. This contrasting response was theoretically established to originate from the differential strain-induced modulation of the activation energy. Critically, applied tensile force thus governs directly both the kinetics and mechanistic pathway of ROMP, selectively promoting cyclic oligomer formation and establishing a molecular-strain-engineering paradigm that transcends conventional ring-strain-driven polymerization.