Geomimetic Hydrothermal Synthesis of Polyimide-Based Covalent Organic Frameworks

Taehyung Kim; Se Hun Joo; Jintaek Gong; Sungho Choi; Ju Hong Min; Yongchul Kim; Geunsik Lee; Eunji Lee; Soojin Park; Sang Kyu Kwak; Hee-Seung Lee; Byeong-Su Kim

doi:10.1002/anie.202113780

Geomimetic Hydrothermal Synthesis of Polyimide-Based Covalent Organic Frameworks

Angew Chem Int Ed Engl. 2022 Jan 21;61(4):e202113780. doi: 10.1002/anie.202113780. Epub 2021 Nov 25.

Authors

Taehyung Kim^{1

2}, Se Hun Joo², Jintaek Gong³, Sungho Choi⁴, Ju Hong Min⁵, Yongchul Kim⁶, Geunsik Lee⁶, Eunji Lee⁵, Soojin Park⁴, Sang Kyu Kwak², Hee-Seung Lee³, Byeong-Su Kim¹

Affiliations

¹ Department of Chemistry, Yonsei University, Seoul, 03722, Republic of Korea.
² School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, 44919, Republic of Korea.
³ Center for Multiscale Chiral Architectures and Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141, Republic of Korea.
⁴ Division of Advanced Material Science, Department of Chemistry, Pohang University of Science and Technology (POSTECH), Pohang, 37673, Republic of Korea.
⁵ School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju, 61005, Republic of Korea.
⁶ Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan, 44919, Republic of Korea.

PMID: 34708501
DOI: 10.1002/anie.202113780

Abstract

Despite its abundance, water is not widely used as a medium for organic reactions. However, under geothermal conditions, water exhibits unique physicochemical properties, such as viscosity and a dielectric constant, and the ionic product become similar to those of common organic solvents. We have synthesized highly crystalline polyimide-based covalent organic frameworks (PICs) under geomimetic hydrothermal conditions. By exploiting triphenylene-2,3,6,7,10,11-hexacarboxylic acid in combination with various aromatic diamines, PICs with various pore dimensions and crystallinities were synthesized. XRD, FT-IR, and DFT calculations revealed that the solubility of the oligomeric intermediates under hydrothermal conditions affected the stacking structures of the crystalline PICs. Furthermore, the synthesized PICs demonstrate promising potential as an anode material in lithium-ion batteries owing to its unique redox-active properties and high surface area.

Keywords: hydrothermal reactions; oligomers; organic anodes; polyimides.

Abstract

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