Linkage conversions in single-crystalline covalent organic frameworks

Baoqiu Yu; Rui-Biao Lin; Gang Xu; Zhi-Hua Fu; Hui Wu; Wei Zhou; Shanfu Lu; Qian-Wen Li; Yucheng Jin; Jing-Hong Li; Zhenguo Zhang; Hailong Wang; Zier Yan; Xiaolin Liu; Kang Wang; Banglin Chen; Jianzhuang Jiang

doi:10.1038/s41557-023-01334-7

Linkage conversions in single-crystalline covalent organic frameworks

Nat Chem. 2024 Jan;16(1):114-121. doi: 10.1038/s41557-023-01334-7. Epub 2023 Sep 18.

Authors

Baoqiu Yu^#¹, Rui-Biao Lin^#², Gang Xu³, Zhi-Hua Fu³, Hui Wu⁴, Wei Zhou⁴, Shanfu Lu⁵, Qian-Wen Li³, Yucheng Jin¹, Jing-Hong Li², Zhenguo Zhang⁵, Hailong Wang⁶, Zier Yan⁷, Xiaolin Liu¹, Kang Wang¹, Banglin Chen⁸, Jianzhuang Jiang⁹

Affiliations

¹ Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing, China.
² MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, IGCME, Sun Yat-Sen University, Guangzhou, China.
³ State Key Laboratory of Structural Chemistry, Fujian Provincial Key Laboratory of Materials and Techniques toward Hydrogen Energy, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, China.
⁴ Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD, USA.
⁵ Beijing Key Laboratory of Bio-Inspired Energy Materials and Devices, School of Space and Environment, Beihang University, Beijing, China.
⁶ Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing, China. hlwang@ustb.edu.cn.
⁷ Rigaku Beijing Corporation, Beijing, China.
⁸ Fujian Provincial Key Laboratory of Polymer Materials, College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, China. banglin.chen@fjnu.edu.cn.
⁹ Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing, China. jianzhuang@ustb.edu.cn.

^# Contributed equally.

PMID: 37723258
DOI: 10.1038/s41557-023-01334-7

Abstract

Single-crystal X-ray diffraction is a powerful characterization technique that enables the determination of atomic arrangements in crystalline materials. Growing or retaining large single crystals amenable to it has, however, remained challenging with covalent organic frameworks (COFs), especially suffering from post-synthetic modifications. Here we show the synthesis of a flexible COF with interpenetrated qtz topology by polymerization of tetra(phenyl)bimesityl-based tetraaldehyde and tetraamine building blocks. The material is shown to be flexible through its large, anisotropic positive thermal expansion along the c axis (α_c = +491 × 10^-6 K^-1), as well as through a structural transformation on the removal of solvent molecules from its pores. The as-synthesized and desolvated materials undergo single-crystal-to-single-crystal transformation by reduction and oxidation of its imine linkages to amine and amide ones, respectively. These redox-induced linkage conversions endow the resulting COFs with improved stability towards strong acid; loading of phosphoric acid leads to anhydrous proton conductivity up to ca. 6.0 × 10^-2 S cm^-1.

Abstract

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