skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

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:
; ORCiD logo; ; ; ; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1461610
Alternate Identifier(s):
OSTI ID: 1477418
Grant/Contract Number:  
AC02-05CH11231; 21603076
Resource Type:
Published Article
Journal Name:
Nature Communications
Additional Journal Information:
Journal Name: Nature Communications Journal Volume: 9 Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; polymer synthesis; polymers; porous materials

Citation Formats

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 Kingdom: N. p., 2018. 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 Kingdom. 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. Tue . "Facile transformation of imine covalent organic frameworks into ultrastable crystalline porous aromatic frameworks". United Kingdom. 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 = 1,
volume = 9,
place = {United Kingdom},
year = {2018},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1038/s41467-018-05462-4

Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Conjugated microporous polymers: design, synthesis and application
journal, January 2013

  • Xu, Yanhong; Jin, Shangbin; Xu, Hong
  • Chemical Society Reviews, Vol. 42, Issue 20
  • DOI: 10.1039/c3cs60160a

Thioether-Based Fluorescent Covalent Organic Framework for Selective Detection and Facile Removal of Mercury(II)
journal, February 2016

  • Ding, San-Yuan; Dong, Ming; Wang, Ya-Wen
  • Journal of the American Chemical Society, Vol. 138, Issue 9
  • DOI: 10.1021/jacs.5b10754

Construction of Crystalline 2D Covalent Organic Frameworks with Remarkable Chemical (Acid/Base) Stability via a Combined Reversible and Irreversible Route
journal, November 2012

  • Kandambeth, Sharath; Mallick, Arijit; Lukose, Binit
  • Journal of the American Chemical Society, Vol. 134, Issue 48
  • DOI: 10.1021/ja308278w

Enhancement of Chemical Stability and Crystallinity in Porphyrin-Containing Covalent Organic Frameworks by Intramolecular Hydrogen Bonds
journal, October 2013

  • Kandambeth, Sharath; Shinde, Digambar Balaji; Panda, Manas K.
  • Angewandte Chemie, Vol. 125, Issue 49
  • DOI: 10.1002/ange.201306775

Chemically Delaminated Free-Standing Ultrathin Covalent Organic Nanosheets
journal, November 2016

  • Khayum, M. Abdul; Kandambeth, Sharath; Mitra, Shouvik
  • Angewandte Chemie International Edition, Vol. 55, Issue 50
  • DOI: 10.1002/anie.201607812

Sequential Pore Wall Modification in a Covalent Organic Framework for Application in Lactic Acid Adsorption
journal, January 2016


Super-hydrophobic covalent organic frameworks for chemical resistant coatings and hydrophobic paper and textile composites
journal, January 2017

  • Mullangi, Dinesh; Shalini, Sorout; Nandi, Shyamapada
  • Journal of Materials Chemistry A, Vol. 5, Issue 18
  • DOI: 10.1039/C7TA01302G

The atom, the molecule, and the covalent organic framework
journal, March 2017


A Facile and General Coating Approach to Moisture/Water-Resistant Metal–Organic Frameworks with Intact Porosity
journal, November 2014

  • Zhang, Wang; Hu, Yingli; Ge, Jin
  • Journal of the American Chemical Society, Vol. 136, Issue 49
  • DOI: 10.1021/ja509960n

Tessellated multiporous two-dimensional covalent organic frameworks
journal, July 2017


Solution Synthesis of Semiconducting Two-Dimensional Polymer via Trimerization of Carbonitrile
journal, July 2017

  • Liu, Jingjing; Zan, Wu; Li, Ke
  • Journal of the American Chemical Society, Vol. 139, Issue 34
  • DOI: 10.1021/jacs.7b05025

Two-dimensional sp 2 carbon–conjugated covalent organic frameworks
journal, August 2017


Molecular docking sites designed for the generation of highly crystalline covalent organic frameworks
journal, February 2016

  • Ascherl, Laura; Sick, Torben; Margraf, Johannes T.
  • Nature Chemistry, Vol. 8, Issue 4
  • DOI: 10.1038/nchem.2444

Ultrastable Imine-Based Covalent Organic Frameworks for Sulfuric Acid Recovery: An Effect of Interlayer Hydrogen Bonding
journal, April 2018

  • Halder, Arjun; Karak, Suvendu; Addicoat, Matthew
  • Angewandte Chemie International Edition, Vol. 57, Issue 20
  • DOI: 10.1002/anie.201802220

Storage of Hydrogen, Methane, and Carbon Dioxide in Highly Porous Covalent Organic Frameworks for Clean Energy Applications
journal, July 2009

  • Furukawa, Hiroyasu; Yaghi, Omar M.
  • Journal of the American Chemical Society, Vol. 131, Issue 25, p. 8875-8883
  • DOI: 10.1021/ja9015765

Ultrathin Two-Dimensional Covalent Organic Framework Nanosheets: Preparation and Application in Highly Sensitive and Selective DNA Detection
journal, June 2017

  • Peng, Yongwu; Huang, Ying; Zhu, Yihan
  • Journal of the American Chemical Society, Vol. 139, Issue 25
  • DOI: 10.1021/jacs.7b04096

Oriented Thin Films of a Benzodithiophene Covalent Organic Framework
journal, March 2014

  • Medina, Dana D.; Werner, Veronika; Auras, Florian
  • ACS Nano, Vol. 8, Issue 4
  • DOI: 10.1021/nn5000223

A Cryogenically Flexible Covalent Organic Framework for Efficient Hydrogen Isotope Separation by Quantum Sieving
journal, November 2013

  • Oh, Hyunchul; Kalidindi, Suresh Babu; Um, Youngje
  • Angewandte Chemie International Edition, Vol. 52, Issue 50
  • DOI: 10.1002/anie.201307443

Synthesis of Ultrafine and Highly Dispersed Metal Nanoparticles Confined in a Thioether-Containing Covalent Organic Framework and Their Catalytic Applications
journal, November 2017

  • Lu, Shuanglong; Hu, Yiming; Wan, Shun
  • Journal of the American Chemical Society, Vol. 139, Issue 47
  • DOI: 10.1021/jacs.7b07918

Unravelling surface and interfacial structures of a metal–organic framework by transmission electron microscopy
journal, February 2017

  • Zhu, Yihan; Ciston, Jim; Zheng, Bin
  • Nature Materials, Vol. 16, Issue 5
  • DOI: 10.1038/nmat4852

Benzoxazole-Linked Ultrastable Covalent Organic Frameworks for Photocatalysis
journal, March 2018

  • Wei, Pi-Feng; Qi, Ming-Zhu; Wang, Zhi-Peng
  • Journal of the American Chemical Society, Vol. 140, Issue 13
  • DOI: 10.1021/jacs.8b00571

Porous, Crystalline, Covalent Organic Frameworks
journal, November 2005

  • Côté, Adrien P.; Benin, Annabelle I.; Ockwig, Nathan W.
  • Science, Vol. 310, Issue 5751, p. 1166-1170
  • DOI: 10.1126/science.1120411

Covalent organic frameworks based on Schiff-base chemistry: synthesis, properties and potential applications
journal, January 2016

  • Segura, José L.; Mancheño, María J.; Zamora, Félix
  • Chemical Society Reviews, Vol. 45, Issue 20
  • DOI: 10.1039/C5CS00878F

Toward Covalent Organic Frameworks Bearing Three Different Kinds of Pores: The Strategy for Construction and COF-to-COF Transformation via Heterogeneous Linker Exchange
journal, May 2017

  • Qian, Cheng; Qi, Qiao-Yan; Jiang, Guo-Fang
  • Journal of the American Chemical Society, Vol. 139, Issue 19
  • DOI: 10.1021/jacs.7b02303

A two-dimensional conjugated aromatic polymer via C–C coupling reaction
journal, January 2017


Moisture-Resistant and Superhydrophobic Metal−Organic Frameworks Obtained via Postsynthetic Modification
journal, April 2010

  • Nguyen, Joseph G.; Cohen, Seth M.
  • Journal of the American Chemical Society, Vol. 132, Issue 13
  • DOI: 10.1021/ja100900c

Conjugated Covalent Organic Frameworks via Michael Addition–Elimination
journal, January 2017

  • Rao, M. Rajeswara; Fang, Yuan; De Feyter, Steven
  • Journal of the American Chemical Society, Vol. 139, Issue 6
  • DOI: 10.1021/jacs.6b12005

Pore surface engineering in covalent organic frameworks
journal, September 2011

  • Nagai, Atsushi; Guo, Zhaoqi; Feng, Xiao
  • Nature Communications, Vol. 2, Issue 1
  • DOI: 10.1038/ncomms1542

Reticular Synthesis of Microporous and Mesoporous 2D Covalent Organic Frameworks
journal, October 2007

  • Côté, Adrien P.; El-Kaderi, Hani M.; Furukawa, Hiroyasu
  • Journal of the American Chemical Society, Vol. 129, Issue 43, p. 12914-12915
  • DOI: 10.1021/ja0751781

Stable, crystalline, porous, covalent organic frameworks as a platform for chiral organocatalysts
journal, September 2015

  • Xu, Hong; Gao, Jia; Jiang, Donglin
  • Nature Chemistry, Vol. 7, Issue 11
  • DOI: 10.1038/nchem.2352

A Photoconductive Covalent Organic Framework: Self-Condensed Arene Cubes Composed of Eclipsed 2D Polypyrene Sheets for Photocurrent Generation
journal, July 2009

  • Wan, Shun; Guo, Jia; Kim, Jangbae
  • Angewandte Chemie International Edition, Vol. 48, Issue 30
  • DOI: 10.1002/anie.200900881

Chemical Conversion of Linkages in Covalent Organic Frameworks
journal, November 2016

  • Waller, Peter J.; Lyle, Steven J.; Osborn Popp, Thomas M.
  • Journal of the American Chemical Society, Vol. 138, Issue 48
  • DOI: 10.1021/jacs.6b08377

β-Ketoenamine-Linked Covalent Organic Frameworks Capable of Pseudocapacitive Energy Storage
journal, October 2013

  • DeBlase, Catherine R.; Silberstein, Katharine E.; Truong, Thanh-Tam
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja409421d

A Belt-Shaped, Blue Luminescent, and Semiconducting Covalent Organic Framework
journal, November 2008

  • Wan, Shun; Guo, Jia; Kim, Jangbae
  • Angewandte Chemie, Vol. 120, Issue 46, p. 8958-8962
  • DOI: 10.1002/ange.200803826

Locking Covalent Organic Frameworks with Hydrogen Bonds: General and Remarkable Effects on Crystalline Structure, Physical Properties, and Photochemical Activity
journal, March 2015

  • Chen, Xiong; Addicoat, Matthew; Jin, Enquan
  • Journal of the American Chemical Society, Vol. 137, Issue 9
  • DOI: 10.1021/ja509602c

Tailor-Made Pore Surface Engineering in Covalent Organic Frameworks: Systematic Functionalization for Performance Screening
journal, June 2015

  • Huang, Ning; Krishna, Rajamani; Jiang, Donglin
  • Journal of the American Chemical Society, Vol. 137, Issue 22
  • DOI: 10.1021/jacs.5b04300

An Aza-Diels–Alder Route to Polyquinolines
journal, January 2015

  • Dibble, David J.; Umerani, Mehran J.; Mazaheripour, Amir
  • Macromolecules, Vol. 48, Issue 3
  • DOI: 10.1021/ma5020726