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<p>Two-dimension covalent organic frameworks (2D COFs) with electrochemical active units exhibit the excellent application prospect in the field of photo-electric materials due to their uniform and adjustable building block, and two-dimensional conjugated π-electron delocalization structure. The effects of the building block size on the COF structure and photo-electric properties of COFs are worth discussing. In this work, TABD-COF was prepared using tri(4-aminophenyl)amine (TAPA) and 1,4-Benzenedicarboxaldehyde (BDA) as two building blocks, while TATP-COF was prepared using tri(4-aminophenyl)amine and 4,4''-<i>p</i>-Terphenyldicarboxaldehyde (TPDA) as two building blocks. The major active unit triphenylamine (TPA) is connected by different number of benzene ring in the covalent organic framework structure, which can endow COF with different channel size, crystal face parameter, band gap, and electrochemical and electrochromic properties. With longer connection group, TATP-COF has larger channel size, crystal cell and band gap. TABD-COF film displays the reversible color change from reddish brown to dark brown, while TATP-COF film reversible color change from yellow to brown. Compared with TATP-COF, TABD-COF shows the higher crystallinity and more regular morphology, which can be attributed to the directional regulation feature of short structural units in reversible polymerization reaction. In addition, TABD-COF film also shows the better electrochromic properties with the contrast of 0.34 and coloring time/bleaching time of 7.1/12.4&#xa0;s, respectively. This work provides a reference method for structure designing of COF based electrochromic materials.</p>

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The influence of building block length on the electrochemical and electrochromic properties of triphenylamine based covalent organic framework

  • 期刊论文

  • 发表日期：

    2025年5月30日

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  • Qiao Chen,
  • Yukun Zhang,
  • Chong Tian,
  • Shanxin Xiong

摘要

Two-dimension covalent organic frameworks (2D COFs) with electrochemical active units exhibit the excellent application prospect in the field of photo-electric materials due to their uniform and adjustable building block, and two-dimensional conjugated π-electron delocalization structure. The effects of the building block size on the COF structure and photo-electric properties of COFs are worth discussing. In this work, TABD-COF was prepared using tri(4-aminophenyl)amine (TAPA) and 1,4-Benzenedicarboxaldehyde (BDA) as two building blocks, while TATP-COF was prepared using tri(4-aminophenyl)amine and 4,4''-p-Terphenyldicarboxaldehyde (TPDA) as two building blocks. The major active unit triphenylamine (TPA) is connected by different number of benzene ring in the covalent organic framework structure, which can endow COF with different channel size, crystal face parameter, band gap, and electrochemical and electrochromic properties. With longer connection group, TATP-COF has larger channel size, crystal cell and band gap. TABD-COF film displays the reversible color change from reddish brown to dark brown, while TATP-COF film reversible color change from yellow to brown. Compared with TATP-COF, TABD-COF shows the higher crystallinity and more regular morphology, which can be attributed to the directional regulation feature of short structural units in reversible polymerization reaction. In addition, TABD-COF film also shows the better electrochromic properties with the contrast of 0.34 and coloring time/bleaching time of 7.1/12.4 s, respectively. This work provides a reference method for structure designing of COF based electrochromic materials.