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<p>Polyenes with an extensively cross-conjugated backbone, namely poly(1,1-vinylene)s or dendralenes, have fascinated chemists owing to their unique opto-electronic properties and reactivities. Existing synthetic strategies rely on coupling vinylic building blocks. Here we report a chain-growth approach that streamlines the synthesis of dendralene skeletons. An in-situ-generated strained [3]cumulene can interact with an organocopper species via its central in-plane π-bond, unlocking a previously unknown 2,3-polymerization pathway. This process rapidly generates cross-conjugated polyenes containing up to ~80–100 consecutive vinylene units on average with well-defined end groups. These π-electron-rich molecules adopt coiled, helical conformations as suggested by spectroscopic analysis, computational modelling and analogy to known foldamer systems, which induces two-photon absorption without compromising visible transparency. Their application in visible-range two-photon lithography with subdiffraction-limit resolution is demonstrated.</p><p></p>

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Chain-growth synthesis of extensively cross-conjugated polyenes

  • 期刊论文

  • 发表日期：

    2025年3月10日

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  • Zi-Yuan Wang,
  • Yi-Ze Xu,
  • Zhanpeng Cui,
  • Luo Zhang,
  • Jia-Yu Lu,
  • Yu-Qing Zheng,
  • Rong Zhu

摘要

Polyenes with an extensively cross-conjugated backbone, namely poly(1,1-vinylene)s or dendralenes, have fascinated chemists owing to their unique opto-electronic properties and reactivities. Existing synthetic strategies rely on coupling vinylic building blocks. Here we report a chain-growth approach that streamlines the synthesis of dendralene skeletons. An in-situ-generated strained [3]cumulene can interact with an organocopper species via its central in-plane π-bond, unlocking a previously unknown 2,3-polymerization pathway. This process rapidly generates cross-conjugated polyenes containing up to ~80–100 consecutive vinylene units on average with well-defined end groups. These π-electron-rich molecules adopt coiled, helical conformations as suggested by spectroscopic analysis, computational modelling and analogy to known foldamer systems, which induces two-photon absorption without compromising visible transparency. Their application in visible-range two-photon lithography with subdiffraction-limit resolution is demonstrated.