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Title: Facile transformation of imine covalent organic frameworks into ultrastable crystalline porous aromatic frameworks

The growing interest in two-dimensional imine-based covalent organic frameworks (COFs) is inspired by their crystalline porous structures and the potential for extensive π-electron delocalization. The intrinsic reversibility and strong polarization of imine linkages, however, leads to insufficient chemical stability and optoelectronic properties. Developing COFs with improved robustness and π-delocalization is highly desirable but remains an unsettled challenge. Here we report a facile strategy that transforms imine-linked COFs into ultrastable porous aromatic frameworks by kinetically fixing the reversible imine linkage via an aza-Diels-Alder cycloaddition reaction. The as-formed, quinoline-linked COFs not only retain crystallinity and porosity, but also display dramatically enhanced chemical stability over their imine-based COF precursors, rendering them among the most robust COFs up-to-date that can withstand strong acidic, basic and redox environment. Owing to the chemical diversity of the cycloaddition reaction and structural tunability of COFs, the pores of COFs can be readily engineered to realize pre-designed surface functionality.
Authors:
 [1] ; ORCiD logo [1] ;  [2] ;  [3] ;  [1] ;  [4] ;  [1] ;  [1] ;  [1] ; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Molecular Foundry
  2. South China Normal Univ., Guangzhou (China). School of Chemistry and Environment
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Molecular Foundry; Zhejiang Univ., Hangzhou (China). Dept. of Chemistry
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Advanced Light Source
Publication Date:
Grant/Contract Number:
AC02-05CH11231; 21603076
Type:
Published Article
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); South China Normal Univ., Guangzhou (China); Zhejiang Univ., Hangzhou (China)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Natural Science Foundation of China (NNSFC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; polymer synthesis; polymers; porous materials
OSTI Identifier:
1461610
Alternate Identifier(s):
OSTI ID: 1477418

Li, Xinle, Zhang, Changlin, Cai, Songliang, Lei, Xiaohe, Altoe, Virginia, Hong, Fang, Urban, Jeffrey J., Ciston, Jim, Chan, Emory M., and Liu, Yi. Facile transformation of imine covalent organic frameworks into ultrastable crystalline porous aromatic frameworks. United States: N. p., Web. doi:10.1038/s41467-018-05462-4.
Li, Xinle, Zhang, Changlin, Cai, Songliang, Lei, Xiaohe, Altoe, Virginia, Hong, Fang, Urban, Jeffrey J., Ciston, Jim, Chan, Emory M., & Liu, Yi. Facile transformation of imine covalent organic frameworks into ultrastable crystalline porous aromatic frameworks. United States. doi:10.1038/s41467-018-05462-4.
Li, Xinle, Zhang, Changlin, Cai, Songliang, Lei, Xiaohe, Altoe, Virginia, Hong, Fang, Urban, Jeffrey J., Ciston, Jim, Chan, Emory M., and Liu, Yi. 2018. "Facile transformation of imine covalent organic frameworks into ultrastable crystalline porous aromatic frameworks". United States. doi:10.1038/s41467-018-05462-4.
@article{osti_1461610,
title = {Facile transformation of imine covalent organic frameworks into ultrastable crystalline porous aromatic frameworks},
author = {Li, Xinle and Zhang, Changlin and Cai, Songliang and Lei, Xiaohe and Altoe, Virginia and Hong, Fang and Urban, Jeffrey J. and Ciston, Jim and Chan, Emory M. and Liu, Yi},
abstractNote = {The growing interest in two-dimensional imine-based covalent organic frameworks (COFs) is inspired by their crystalline porous structures and the potential for extensive π-electron delocalization. The intrinsic reversibility and strong polarization of imine linkages, however, leads to insufficient chemical stability and optoelectronic properties. Developing COFs with improved robustness and π-delocalization is highly desirable but remains an unsettled challenge. Here we report a facile strategy that transforms imine-linked COFs into ultrastable porous aromatic frameworks by kinetically fixing the reversible imine linkage via an aza-Diels-Alder cycloaddition reaction. The as-formed, quinoline-linked COFs not only retain crystallinity and porosity, but also display dramatically enhanced chemical stability over their imine-based COF precursors, rendering them among the most robust COFs up-to-date that can withstand strong acidic, basic and redox environment. Owing to the chemical diversity of the cycloaddition reaction and structural tunability of COFs, the pores of COFs can be readily engineered to realize pre-designed surface functionality.},
doi = {10.1038/s41467-018-05462-4},
journal = {Nature Communications},
number = ,
volume = 9,
place = {United States},
year = {2018},
month = {7}
}

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