Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 59, Issue 36, Pages 15750-15758Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202007372
Keywords
covalent organic frameworks; eutectic salt mixtures; ionothermal synthesis; polyimides
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Funding
- Federal Ministry of Education and Research [FKZ: 03XP0030C]
- Max Planck Society
- Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) [358283783-SFB 1333]
- ERC [639233]
- Cluster of Excellence e-conversion [EXC 2089/1-390776260]
- Center for Nanoscience (CeNS)
- MPI-FKF Stuttgart
- Projekt DEAL
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Covalent organic frameworks (COFs) are an extensively studied class of porous materials, which distinguish themselves from other porous polymers in their crystallinity and high degree of modularity, enabling a wide range of applications. COFs are most commonly synthesized solvothermally, which is often a time-consuming process and restricted to well-soluble precursor molecules. Synthesis of polyimide-linked COFs (PI-COFs) is further complicated by the poor reversibility of the ring-closing reaction under solvothermal conditions. Herein, we report the ionothermal synthesis of crystalline and porous PI-COFs in zinc chloride and eutectic salt mixtures. This synthesis does not require soluble precursors and the reaction time is significantly reduced as compared to standard solvothermal synthesis methods. In addition to applying the synthesis to previously reported imide COFs, a new perylene-based COF was also synthesized, which could not be obtained by the classical solvothermal route. In situ high-temperature XRPD analysis hints to the formation of precursor-salt adducts as crystalline intermediates, which then react with each other to form the COF.
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