Covalent Organic Frameworks with Irreversible Linkages via Reductive Cyclization of Imines
Abstract
Covalent organic frameworks (COFs) show great potential for many advanced applications on account of their structural uniqueness. To address the synthetic challenges, facile chemical routes to engineer the porosity, crystallinity, and functionality of COFs are highly sought after. Herein, we report a synthetic approach that employs the Cadogan reaction to introduce nitrogen-containing heterocycles as the linkages in the framework. Irreversible indazole and benzimidazolylidene (BIY) linkages are introduced into COFs for the first time via phosphine-induced reductive cyclization of the common imine linkages following either stepwise or one-pot reaction protocols. Further, the successful linkage transformation introduces new functionalities, as demonstrated in the case of BIY-COF, which displays excellent intrinsic proton conductivity without the need of impregnation with external proton transfer reagents. Such a general strategy will open the window to a broader class of functional porous crystalline materials.
- Authors:
-
[1];
[1];
[3];
[1];
[1];
[1]
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
- Univ. of California, Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1893886
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 144; Journal Issue: 22; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cadogan reaction; Porous materials; Proton conductivity; Reductive cyclization; Chemical structure; Covalent organic frameworks; Cyclization; Diffraction
Citation Formats
Yang, Sizhuo, Yang, Chongqing, Dun, Chaochao, Mao, Haiyan, Khoo, Rebecca Shu Hui, Klivansky, Liana M., Reimer, Jeffrey A., Urban, Jeffrey J., Zhang, Jian, and Liu, Yi. Covalent Organic Frameworks with Irreversible Linkages via Reductive Cyclization of Imines. United States: N. p., 2022.
Web. doi:10.1021/jacs.2c02405.
Yang, Sizhuo, Yang, Chongqing, Dun, Chaochao, Mao, Haiyan, Khoo, Rebecca Shu Hui, Klivansky, Liana M., Reimer, Jeffrey A., Urban, Jeffrey J., Zhang, Jian, & Liu, Yi. Covalent Organic Frameworks with Irreversible Linkages via Reductive Cyclization of Imines. United States. https://doi.org/10.1021/jacs.2c02405
Yang, Sizhuo, Yang, Chongqing, Dun, Chaochao, Mao, Haiyan, Khoo, Rebecca Shu Hui, Klivansky, Liana M., Reimer, Jeffrey A., Urban, Jeffrey J., Zhang, Jian, and Liu, Yi. Fri .
"Covalent Organic Frameworks with Irreversible Linkages via Reductive Cyclization of Imines". United States. https://doi.org/10.1021/jacs.2c02405. https://www.osti.gov/servlets/purl/1893886.
@article{osti_1893886,
title = {Covalent Organic Frameworks with Irreversible Linkages via Reductive Cyclization of Imines},
author = {Yang, Sizhuo and Yang, Chongqing and Dun, Chaochao and Mao, Haiyan and Khoo, Rebecca Shu Hui and Klivansky, Liana M. and Reimer, Jeffrey A. and Urban, Jeffrey J. and Zhang, Jian and Liu, Yi},
abstractNote = {Covalent organic frameworks (COFs) show great potential for many advanced applications on account of their structural uniqueness. To address the synthetic challenges, facile chemical routes to engineer the porosity, crystallinity, and functionality of COFs are highly sought after. Herein, we report a synthetic approach that employs the Cadogan reaction to introduce nitrogen-containing heterocycles as the linkages in the framework. Irreversible indazole and benzimidazolylidene (BIY) linkages are introduced into COFs for the first time via phosphine-induced reductive cyclization of the common imine linkages following either stepwise or one-pot reaction protocols. Further, the successful linkage transformation introduces new functionalities, as demonstrated in the case of BIY-COF, which displays excellent intrinsic proton conductivity without the need of impregnation with external proton transfer reagents. Such a general strategy will open the window to a broader class of functional porous crystalline materials.},
doi = {10.1021/jacs.2c02405},
journal = {Journal of the American Chemical Society},
number = 22,
volume = 144,
place = {United States},
year = {Fri May 27 00:00:00 EDT 2022},
month = {Fri May 27 00:00:00 EDT 2022}
}
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