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Engineering Intralayer Anisotropy in Covalent Organic Frameworks.

Yao Chai1, Yanmei Chen2, Shu-He Han1

  • 1Department of Applied Physics, The Hong Kong Polytechnic University, Kowloon, Hong Kong, 999077, China.

Angewandte Chemie (International Ed. in English)
|December 20, 2025
PubMed
Summary

Researchers engineered covalent organic frameworks (COFs) with tunable anisotropy using a mixed-linker strategy. Shortening linkers enhanced charge carrier mobility and photocatalytic efficiency for NADH oxidation and near-infrared applications.

Keywords:
Charge transportCovalent organic frameworksIntralayer anisotropyNAD+ oxidationPhotocatalysis

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Area of Science:

  • Materials Science
  • Nanotechnology
  • Photocatalysis

Background:

  • Controlling intralayer anisotropy in 2D covalent organic frameworks (COFs) is crucial for advanced materials design.
  • Existing methods often lack precise control over anisotropy, limiting performance in applications like photocatalysis.

Purpose of the Study:

  • To develop a novel mixed-linker strategy for precise in-plane anisotropy tuning in COFs.
  • To investigate the impact of linker length on electronic properties and photocatalytic activity.

Main Methods:

  • Synthesized 1D nanoribbons using 8-connected pyrene/triphenylamine and 4-connected ETTA monomers.
  • Longitudinally stitched nanoribbons with diamines of varying lengths to tune anisotropy.
  • Characterized material properties and evaluated photocatalytic performance in NADH oxidation and near-infrared light applications.

Main Results:

  • Shortening linkers (T-COF-1 vs. T-COF-2) induced strain, enhancing π-electron delocalization and quadrupling charge carrier mobility.
  • T-COF-1 achieved 93.81% conversion efficiency in visible-light NADH oxidation, a 4.26-fold improvement.
  • Demonstrated significant activity under near-infrared light (14.67% conversion), indicating potential for photodynamic therapy.

Conclusions:

  • Established interchain covalent proximity as a key design principle for high-performance COF photocatalysts.
  • The developed strategy enables rational engineering of COFs for enhanced solar energy conversion and biomedical applications.
  • Tunable anisotropy in COFs opens new avenues for efficient photocatalysis and photodynamic therapy.