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
- Chinese Journal of Polymer Science Vol. 44, Issue 8, Pages: 2395-2402(2026)
- 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：
- DOI：10.1007/s10118-026-3647-0
  CLC：
- Received：30 January 2026，
  
  Accepted：09 March 2026，
  
  Online First：03 June 2026，
  
  Published：15 August 2026
- 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

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