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

Journal Article · · Nature Communications
 [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

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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); USDOE
Grant/Contract Number:
AC02-05CH11231; 21603076
OSTI ID:
1461610
Alternate ID(s):
OSTI ID: 1477418
Journal Information:
Nature Communications, Vol. 9; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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The Chemistry of Reticular Framework Nanoparticles: MOF, ZIF, and COF Materials journal February 2020
Rapid Synthesis of High Surface Area Imine‐Linked 2D Covalent Organic Frameworks by Avoiding Pore Collapse During Isolation journal November 2019
Opportunities of Covalent Organic Frameworks for Advanced Applications journal November 2018
The Imine‐Based COF TpPa‐1 as an Efficient Cooling Adsorbent That Can Be Regenerated by Heat or Light journal August 2019
Designed Synthesis of a 2D Porphyrin‐Based sp 2 Carbon‐Conjugated Covalent Organic Framework for Heterogeneous Photocatalysis journal February 2019
2D and 3D Porphyrinic Covalent Organic Frameworks: The Influence of Dimensionality on Functionality journal January 2020
Designed Synthesis of a 2D Porphyrin‐Based sp 2 Carbon‐Conjugated Covalent Organic Framework for Heterogeneous Photocatalysis journal May 2019
Tailoring Covalent Organic Frameworks To Capture Water Contaminants journal February 2019
A Versatile Approach to Dynamic Amide Bond Formation with Imine Nucleophiles journal April 2020
Stable Covalent Organic Frameworks for Photochemical Applications journal June 2019
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Porous Covalent Organic Gels: Design, Synthesis and Fluoroquinolones Adsorption journal December 2018
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Postsynthetic functionalization of covalent organic frameworks journal August 2019
2D and 3D Porphyrinic Covalent Organic Frameworks: The Influence of Dimensionality on Functionality journal January 2020
Opportunities of Covalent Organic Frameworks for Advanced Applications journal November 2018
BODIPY-Decorated Nanoscale Covalent Organic Frameworks for Photodynamic Therapy journal April 2019
Porous Aromatic Frameworks as a Platform for Multifunctional Applications journal February 2019