Multistep Solid-State Organic Synthesis of Carbamate-Linked Covalent Organic Frameworks.

Lyle, Steven J.; Osborn Popp, Thomas M.; Waller, Peter J.; Pei, Xiaokun; Reimer, Jeffrey A.; Yaghi, Omar M

doi:10.1021/jacs.9b04731

Multistep Solid-State Organic Synthesis of Carbamate-Linked Covalent Organic Frameworks.

Journal Article · Fri Jun 21 00:00:00 EDT 2019 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.9b04731· OSTI ID:1650066

Lyle, Steven J. ^[1]; Osborn Popp, Thomas M. ^[1]; Waller, Peter J. ^[1]; Pei, Xiaokun ^[1]; Reimer, Jeffrey A. ^[1]; Yaghi, Omar M ^[2]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); King Saud Univ., Riyadh (Saudi Arabia)

Herein, we demonstrate the first example of a multistep solid-state organic synthesis, in which a new imine-linked two-dimensional covalent organic framework (COF-170, 1) was transformed through three consecutive postsynthetic modifications into porous, crystalline cyclic carbamate and thiocarbamate-linked frameworks. These linkages are previously unreported and inaccessible through de novo synthesis. While not altering the overall connectivity of the framework, these chemical transformations induce significant conformational and structural changes at each step, highlighting the key importance of noncovalent interactions and conformational flexibility to COF crystallinity and porosity. These transformations were assessed using ¹⁵N multiCP-MAS NMR spectroscopy, providing the first quantitation of yields in COF postsynthetic modification reactions, as well as of amine defect sites in imine-linked COFs. This multistep COF linkage postsynthetic modification represents a significant step toward bringing the precision of organic solution-phase synthesis to extended solid-state compounds.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1650066

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 28 Vol. 141; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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