Synthesis of three-dimensional covalent organic frameworks through a symmetry reduction strategy

Jianhong Chang; Zeyue Zhang; Haorui Zheng; Hui Li; Jinquan Suo; Chunqing Ji; Fenqian Chen; Shipeng Zhang; Zitao Wang; Valentin Valtchev; Shilun Qiu; Junliang Sun; Qianrong Fang

doi:10.1038/s41557-024-01715-6

Synthesis of three-dimensional covalent organic frameworks through a symmetry reduction strategy

Nat Chem. 2025 Jan 8. doi: 10.1038/s41557-024-01715-6. Online ahead of print.

Authors

Jianhong Chang^#¹, Zeyue Zhang^#², Haorui Zheng^#¹, Hui Li³, Jinquan Suo¹, Chunqing Ji⁴, Fenqian Chen¹, Shipeng Zhang², Zitao Wang¹, Valentin Valtchev^{5

6}, Shilun Qiu¹, Junliang Sun⁷, Qianrong Fang⁸

Affiliations

¹ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, People's Republic of China.
² College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing, People's Republic of China.
³ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, People's Republic of China. [email protected].
⁴ Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore, Singapore.
⁵ Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, People's Republic of China.
⁶ Laboratoire Catalyse et Spectrochimie, Normandie Université, ENSICAEN, UNICAEN, CNRS, Caen, France.
⁷ College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing, People's Republic of China. [email protected].
⁸ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, People's Republic of China. [email protected].

^# Contributed equally.

PMID: 39779972
DOI: 10.1038/s41557-024-01715-6

Abstract

Three-dimensional (3D) covalent organic frameworks (COFs) hold significant promise for a variety of applications. However, conventional design approaches using regular building blocks limit the structural diversity of 3D COFs. Here we design and synthesize two 3D COFs, designated as JUC-644 and JUC-645, through a methodology that relies on using eight-connected building blocks with reduced symmetry. Their structures are solved using continuous rotation electron diffraction and high-resolution transmission electron microscopy, which reveal a unique linkage with a double chain structure, a rare phenomenon in COFs. We deconstruct these structures into [4 + 3(+ 2)]-c nets, which leads to six different topologies. Furthermore, JUC-644 demonstrates high adsorption capacity for C₃H₈ and n-C₄H₁₀ (11.28 and 10.45 mmol g^-1 at 298 K and 1 bar, respectively), surpassing most known porous materials, with notable selectivity for C₃H₈/C₂H₆ and n-C₄H₁₀/C₂H₆. This approach opens avenues for designing intricate architectures and shows the potential of COFs in C₂H₆ recovery from natural gas liquids.

Abstract

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