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Published on: July 10, 2017

Breaking π-π Stacking in One-Dimensional Covalent Organic Frameworks.

Haoran Xia1, Yinghua Jin2, Zhong-Yuan Lu3

  • 1School of Chemistry, Southwest Jiaotong University, Chengdu, China.

Angewandte Chemie (International Ed. in English)
|June 4, 2026
PubMed
Summary
This summary is machine-generated.

Sterically enforced monomers break interlayer stacking in 1D covalent organic frameworks (COFs), enhancing aromatic domain accessibility. This design enables superior iodine adsorption, showcasing a new strategy for high-performance COF materials.

Keywords:
covalent organic frameworksinterlayer interactionspore utilizationsteric hindranceπ‐charge distribution

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Area of Science:

  • Materials Science
  • Chemistry
  • Nanotechnology

Background:

  • Covalent organic frameworks (COFs) often use functional groups for targeted properties.
  • The intrinsic aromatic backbones of COFs are underexplored due to limited accessibility from π-π stacking.
  • Interlayer π-π stacking typically hinders the full utilization of COF aromatic domains.

Purpose of the Study:

  • To investigate a steric-hindrance-driven strategy for breaking interlayer π-π stacking in 1D COFs.
  • To enhance the accessibility of aromatic domains within COF structures.
  • To improve the adsorption performance of COFs by exposing backbone π electrons.

Main Methods:

  • Assembly of 1D COFs (TFPE-MDA, TFPB-MDA) using sterically enforced non-coplanar monomers.
  • Electron population analysis to verify π-electron distribution.
  • Iodine-vapor adsorption measurements.
  • Spectroscopic characterizations (FTIR, Raman, XPS) and theoretical calculations.

Main Results:

  • Steric hindrance successfully broke interlayer π-π stacking, exposing aromatic π electrons.
  • High iodine (I2) uptake capacities were achieved: 4.80 g·g-1 for TFPE-MDA and 5.61 g·g-1 for TFPB-MDA.
  • Characterizations confirmed I···π interactions between adsorbed I2 and the COF aromatic moieties.

Conclusions:

  • A novel design strategy using sterically enforced non-coplanar monomers effectively breaks interlayer π-π stacking in COFs.
  • This approach enhances the accessibility and utilization of intrinsic π electrons in COF backbones.
  • The developed COFs demonstrate superior adsorption performance, particularly for iodine uptake.