Managing Interpenetration in 3D Covalent Organic Frameworks with Spatial-aromatic Building Blocks

Zhen-Yang Hu; Fu-Xiang Wen; Xiao-Yi Xu; Ning Huang

doi:10.1007/s10118-026-3647-0

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Managing Interpenetration in 3D Covalent Organic Frameworks with Spatial-aromatic Building Blocks

RAPID COMMUNICATION | Updated：2026-06-04

- Managing Interpenetration in 3D Covalent Organic Frameworks with Spatial-aromatic Building Blocks
- Managing Interpenetration in 3D Covalent Organic Frameworks with Spatial-aromatic Building Blocks
- Chinese Journal of Polymer Science 2026年44卷第8期页码：2395-2402
- Affiliations：
  
  State Key Laboratory of Silicon and Advanced Semiconductor Materials, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310058, China
- Author bio：
  
  xxyzsq@zju.edu.cn (X.Y.X.)
  nhuang@zju.edu.cn (N.H.)
- Funds：
  
  This work was financially supported by the National Key R&D Program of China (No. 2022YFE0130700), the National Natural Science Foundation of China (No. 22375173), the China Postdoctoral Science Foundation (No. 2025M780159), and Postdoctoral Fellowship Program of CPSF (No. GZB20250042). The authors thank Shenghai Chang at the Center of Cyro-Electron Microscopy (CCEM), Zhejiang University, for his technical assistance with the Cyro-TEM.;The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-026-3647-0.The related data for this paper are available in the Science Data Bank (ScienceDB) database at (https://doi.org/10.57760/sciencedb.j00189.00046).
- DOI：10.1007/s10118-026-3647-0
  中图分类号：
- 收稿：2026-01-30，
  
  录用：2026-03-09，
  
  网络首发：2026-06-03，
  
  纸质出版：2026-08-15
- Accepted：
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Hu, Z. Y.; Wen, F. X.; Xu, X. Y.; Huang, N. Managing interpenetration in 3D covalent organic frameworks with spatial-aromatic building blocks. Chinese J. Polym. Sci. 2026, 44, 2395–2402

Zhen-Yang Hu, Fu-Xiang Wen, Xiao-Yi Xu, et al. Managing Interpenetration in 3D Covalent Organic Frameworks with Spatial-aromatic Building Blocks[J]. Chinese Journal of Polymer Science, 2026, 44(8): 2395-2402.
Hu, Z. Y.; Wen, F. X.; Xu, X. Y.; Huang, N. Managing interpenetration in 3D covalent organic frameworks with spatial-aromatic building blocks. Chinese J. Polym. Sci. 2026, 44, 2395–2402 DOI： 10.1007/s10118-026-3647-0.

Zhen-Yang Hu, Fu-Xiang Wen, Xiao-Yi Xu, et al. Managing Interpenetration in 3D Covalent Organic Frameworks with Spatial-aromatic Building Blocks[J]. Chinese Journal of Polymer Science, 2026, 44(8): 2395-2402. DOI： 10.1007/s10118-026-3647-0.

摘要

Using a 6-connected triangular prismatic amine building block

an isoreticular pair of 3D COFs with

acs

topology was synthesized. The COF constructed from a planar-aromatic aldehyde building block exhibited a lower degree of interpenetration (2-fold) compared to its counterpart derived from a spatial-aromatic aldehyde building block (6-fold).

Abstract

The regulation of interpenetration in three-dimensional covalent organic frameworks (3D COFs) poses a fundamental challenge while offering a powerful means to engineer their pore environments. In this study

we demonstrate that the geometry and electronic character of linear linkers are decisive for achieving such control. Using a rigid

sterically extended 6-connected trigonal prismatic amine building block

we synthesized an isoreticular pair of

acs

-topology 3D COFs to compare the influence of a fully aromatic linker. The resulting frameworks

tris(trimethyl-bis-4-aminophenylphenyl)benzene (TTAPB)- terephthalaldehyde (TPA)-COF and TTAPB-C

C-diformyl-

-carborane (DFCB)-COF

exhibited dramatically different degrees of interpenetration

6-fold and 2-fold

respectively. This contrast originates directly from the linker core; the planar

-conjugated TPA promotes dense

multifold interpenetration

whereas the globular

electron-deficient carborane introduces steric and electronic constraints that strongly limit network replication. Consequently

the difference in the interpenetration dictates the distinct porosity and gas adsorption behavior. By elucidating the structure-determining roles of monomer geometry and electronic properties

this work establishes a rational

design principle for programming interpenetration and porosity in 3D extended frameworks.

关键词

Keywords

references

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