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<p>Conductive two-dimensional covalent organic frameworks (2D COFs) possess intrinsic π–conjugation and long-range order, yet their electrical performance in thin-film devices remains constrained by grain boundaries and amorphous regions that interrupt charge transport. Here we report a simple and scalable strategy to overcome these limitations by bridging polycrystalline COF domains with molecularly dispersed conjugated polymers (CPs). Guided by electronic alignment, geometric compatibility, and chain-length criteria, we identify COF–CP combinations that exhibit markedly enhanced conductivity when assembled into heterostructures. By demonstrating that electrical property enhancement occurs only below the CP crystallization threshold, we show that bridging CPs require short-range ordered or near-amorphous configurations to effectively span COF grains and establish continuous transport pathways. This approach is compatible with wafer-scale fabrication and enables ppb-level NO<sub>2</sub> sensing by coupling COF porosity with CP-mediated charge transport. Our results establish a rational polymer-bridging strategy for COF-based electronic materials and identify key design parameters for its extension to other COF–CP systems.</p>

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Molecular bridge engineering in covalent organic frameworks for enhanced electronic transport

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2026年7月1日

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  • Seong-Wook Kim,
  • Jeong-Min Seo,
  • Byeongsik Yoon,
  • Joaquín Calbo,
  • Seunghyeon Jeon,
  • Seungju Kang,
  • Tae Woong Yoon,
  • Jaehoon Lee,
  • Jiyun Lee,
  • Hoimin Kim,
  • Sung Yun Son,
  • Giwook Lee,
  • Sungjoo Lee,
  • Yeong Don Park,
  • Jongkook Hwang,
  • Boseok Kang

摘要

Conductive two-dimensional covalent organic frameworks (2D COFs) possess intrinsic π–conjugation and long-range order, yet their electrical performance in thin-film devices remains constrained by grain boundaries and amorphous regions that interrupt charge transport. Here we report a simple and scalable strategy to overcome these limitations by bridging polycrystalline COF domains with molecularly dispersed conjugated polymers (CPs). Guided by electronic alignment, geometric compatibility, and chain-length criteria, we identify COF–CP combinations that exhibit markedly enhanced conductivity when assembled into heterostructures. By demonstrating that electrical property enhancement occurs only below the CP crystallization threshold, we show that bridging CPs require short-range ordered or near-amorphous configurations to effectively span COF grains and establish continuous transport pathways. This approach is compatible with wafer-scale fabrication and enables ppb-level NO2 sensing by coupling COF porosity with CP-mediated charge transport. Our results establish a rational polymer-bridging strategy for COF-based electronic materials and identify key design parameters for its extension to other COF–CP systems.