Synthesis of 12-Connected Three-Dimensional Covalent Organic Framework with lnj Topology

Zonglong Li; Guojie Xu; Chenxi Zhang; Shuan Ma; Yaxin Jiang; Hao Xiong; Guo Tian; Yanzhou Wu; Yen Wei; Xiao Chen; Yang Yang; Fei Wei

doi:10.1021/jacs.3c12995

Synthesis of 12-Connected Three-Dimensional Covalent Organic Framework with lnj Topology

J Am Chem Soc. 2024 Feb 21;146(7):4327-4332. doi: 10.1021/jacs.3c12995. Epub 2024 Jan 26.

Authors

Zonglong Li¹, Guojie Xu², Chenxi Zhang^{1

3

4}, Shuan Ma⁵, Yaxin Jiang¹, Hao Xiong¹, Guo Tian¹, Yanzhou Wu⁶, Yen Wei², Xiao Chen¹, Yang Yang⁷, Fei Wei^{1

3}

Affiliations

¹ Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China.
² Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology of the Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, China.
³ Ordos Laboratory, Ordos, Inner Mongolia 017010, China.
⁴ Institute for Carbon Neutrality, Tsinghua University, Beijing 100084, China.
⁵ National Center for Electron Microscopy in Beijing, School of Materials Science and Engineering, The State Key Laboratory of New Ceramics and Fine Processing, Key Laboratory of Advanced Materials (MOE), Tsinghua University, Beijing 100084, China.
⁶ CAS Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Research Center for Coastal Environmental Engineering and Technology, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003, China.
⁷ Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China.

PMID: 38277433
DOI: 10.1021/jacs.3c12995

Abstract

The structural exploration of three-dimensional covalent organic frameworks (3D COFs) is of great significance to the development of COF materials. Different from structurally diverse MOFs, which have a variety of connectivity (3-24), now the valency of 3D COFs is limited to only 4, 6, and 8. Therefore, the exploration of organic building blocks with higher connectivity is a necessary path to broaden the scope of 3D COF structures. Herein, for the first time, we have designed and synthesized a 12-connected triptycene-based precursor (triptycene-12-CHO) with 12 symmetrical distributions of aldehyde groups, which is also the highest valency reported until now. Based on this unique 12-connected structure, we have successfully prepared a novel 3D COF with lnj topology (termed 3D-lnj-COF). The as-synthesized 3D COF exhibits honeycomb main pores and permanent porosity with a Brunauer-Emmett-Teller surface area of 1159.6 m² g^-1. This work not only provides a strategy for synthesizing precursors with a high connectivity but also provides inspiration for enriching the variety of 3D COFs.