TY - JOUR
T1 - Postsynthetic Modification of a Covalent Organic Framework Achieved via Strain-Promoted Cycloaddition
AU - Li, Kelvin
AU - Wong, Naomi K.
AU - Strauss, Michael J.
AU - Evans, Austin M.
AU - Matsumoto, Michio
AU - Dichtel, William R.
AU - Adronov, Alex
N1 - Funding Information:
Financial support for this work was provided by the Natural Science and Engineering Research Council of Canada (NSERC). K.L. is grateful for support through the Ontario Graduate Fellowship (OGF) program. N.K.W. is grateful for support through the NSERC program. This work was also funded by the Army Research Office through the Multidisciplinary University Research Initiative (MURI;W911NF-15-1-0447 to W.R.D.). M.J.S. was supported by the National Science Foundation (NSF) through the Graduate Research Fellowship Program (GRFP) under Grant No. DGE-1842165 and by the Ryan Fellowship and the International Institute for Nanotechnology. A.M.E. was supported by the National Science Foundation (NSF) through the Graduate Research Fellowship Program (GRFP) under Grant No. DGE-1324585.
Funding Information:
Financial support for this work was provided by the Natural Science and Engineering Research Council of Canada (NSERC). K.L. is grateful for support through the Ontario Graduate Fellowship (OGF) program. N.K.W. is grateful for support through the NSERC program. This work was also funded by the Army Research Office through the Multidisciplinary University Research Initiative (MURI;W911NF-15-1-0447, to W.R.D.). M.J.S. was supported by the National Science Foundation (NSF) through the Graduate Research Fellowship Program (GRFP) under Grant No. DGE-1842165 and by the Ryan Fellowship and the International Institute for Nanotechnology. A.M.E. was supported by the National Science Foundation (NSF) through the Graduate Research Fellowship Program (GRFP) under Grant No. DGE-1324585.
Publisher Copyright:
© 2021 American Chemical Society.
PY - 2021/1/20
Y1 - 2021/1/20
N2 - Two-dimensional covalent organic frameworks (2D COFs) are layered, structurally regular, and permanently porous macromolecules. When reactive groups are embedded into a COF structure, subsequent chemical reactions can be performed following polymerization. As such, a postsynthetic modification (PSM) strategy provides diverse materials from a single set of COF monomers and polymerization protocols. Here, we report the synthesis of an asymmetric dibenzocyclooctyne-containing imine-linked 2D COF, which readily undergoes strain-promoted azide-alkyne cycloaddition (SPAAC) reactions without catalyst under mild and dilute conditions. This approach was used to quantitatively decorate the COF lattice with alkyl chains and amines, all without the need for exogenous species. Functionalization may result in spontaneous delamination of bulk COF materials into solution-stable sheets, demonstrating the utility of this technique. As such, this platform is useful for postsynthetic functionalization with sensitive chemical functionalities that are not amenable to direct polymerization or existing PSM strategies.
AB - Two-dimensional covalent organic frameworks (2D COFs) are layered, structurally regular, and permanently porous macromolecules. When reactive groups are embedded into a COF structure, subsequent chemical reactions can be performed following polymerization. As such, a postsynthetic modification (PSM) strategy provides diverse materials from a single set of COF monomers and polymerization protocols. Here, we report the synthesis of an asymmetric dibenzocyclooctyne-containing imine-linked 2D COF, which readily undergoes strain-promoted azide-alkyne cycloaddition (SPAAC) reactions without catalyst under mild and dilute conditions. This approach was used to quantitatively decorate the COF lattice with alkyl chains and amines, all without the need for exogenous species. Functionalization may result in spontaneous delamination of bulk COF materials into solution-stable sheets, demonstrating the utility of this technique. As such, this platform is useful for postsynthetic functionalization with sensitive chemical functionalities that are not amenable to direct polymerization or existing PSM strategies.
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U2 - 10.1021/jacs.0c11811
DO - 10.1021/jacs.0c11811
M3 - Article
C2 - 33410702
AN - SCOPUS:85099621029
VL - 143
SP - 649
EP - 656
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 2
ER -