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      A general design approach toward covalent organic frameworks for highly efficient electrochemiluminescence

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          Abstract

          Electrochemiluminescence (ECL) plays a key role in analysis and sensing because of its high sensitivity and low background. Its wide applications are however limited by a lack of highly tunable ECL luminophores. Here we develop a scalable method to design ECL emitters of covalent organic frameworks (COFs) in aqueous medium by simultaneously restricting the donor and acceptor to the COFs’ tight electron configurations and constructing high-speed charge transport networks through olefin linkages. This design allows efficient intramolecular charge transfer for strong ECL, and no exogenous poisonous co-reactants are needed. Olefin-linked donor-acceptor conjugated COFs, systematically synthesized by combining non-ECL active monomers with C 2v or C 3v symmetry, exhibit strong ECL signals, which can be boosted by increasing the chain length and conjugation of monomers. The present concept demonstrates that the highly efficient COF-based ECL luminophores can be precisely designed, providing a promising direction toward COF-based ECL phosphors.

          Abstract

          Electrochemiluminescence (ECL) plays a key role in analysis and sensing but its application is limited by a lack of highly tunable luminophores. Here, the authors demonstrate the design of high efficient ECL luminophores of covalent organic frameworks (COFs) in aqueous media by simultaneously restricting the donor and acceptor to the COFs’ electron configurations and constructing charge transport networks through olefin linkages.

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          Porous, crystalline, covalent organic frameworks.

          Covalent organic frameworks (COFs) have been designed and successfully synthesized by condensation reactions of phenyl diboronic acid {C6H4[B(OH)2]2} and hexahydroxytriphenylene [C18H6(OH)6]. Powder x-ray diffraction studies of the highly crystalline products (C3H2BO)6.(C9H12)1 (COF-1) and C9H4BO2 (COF-5) revealed expanded porous graphitic layers that are either staggered (COF-1, P6(3)/mmc) or eclipsed (COF-5, P6/mmm). Their crystal structures are entirely held by strong bonds between B, C, and O atoms to form rigid porous architectures with pore sizes ranging from 7 to 27 angstroms. COF-1 and COF-5 exhibit high thermal stability (to temperatures up to 500 degrees to 600 degrees C), permanent porosity, and high surface areas (711 and 1590 square meters per gram, respectively).
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            Covalent Organic Frameworks: Structures, Synthesis, and Applications

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              Covalent Organic Frameworks: Chemistry beyond the Structure

              Covalent organic frameworks (COFs) represent a new field of rapidly growing chemical research that takes direct inspiration from diverse covalent bonds existing between atoms. The success of linking atoms in two and three dimensions to construct extended framework structures moved the chemistry of COFs beyond the structures to methodologies, highlighting the possibility of prospective applications. Although structure to property relation in COFs has led to fascinating properties, chemical stability, processability and scalability were some of the important challenges that needed to be overcome for their successful implementation. In this Perspective, we take a closer look at the growth of COFs from mere supramolecular structures to potential industrializable materials.
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                Author and article information

                Contributors
                jdqiu@ncu.edu.cn
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                5 August 2021
                5 August 2021
                2021
                : 12
                : 4735
                Affiliations
                [1 ]GRID grid.260463.5, ISNI 0000 0001 2182 8825, College of Chemistry, , Nanchang University, ; Nanchang, 330031 China
                [2 ]GRID grid.495255.a, College of Materials and Chemical Engineering, , Pingxiang University, ; Pingxiang, 337055 China
                Author information
                https://orcid.org/http://orcid.org/0000-0002-6793-9499
                Article
                25013
                10.1038/s41467-021-25013-8
                8342611
                34354067
                ca3dc777-21de-4d3f-8bb7-cdac603a2215
                © The Author(s) 2021

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 13 April 2021
                : 14 July 2021
                Funding
                Funded by: FundRef https://doi.org/10.13039/501100001809, National Natural Science Foundation of China (National Science Foundation of China);
                Award ID: 22036003, 21775065, and 21976077
                Award Recipient :
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                © The Author(s) 2021

                Uncategorized
                polymers,electronic properties and materials,organic molecules in materials science

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