Chemical Conversion of Linkages in Covalent Organic Frameworks

Peter J. Waller; Steven J. Lyle; Thomas M. Osborn Popp; Christian S. Diercks; Jeffrey A. Reimer; Omar M. Yaghi

doi:10.1021/jacs.6b08377

Chemical Conversion of Linkages in Covalent Organic Frameworks

Peter J. Waller
, Steven J. Lyle
, Thomas M. Osborn Popp
, Christian S. Diercks
, Jeffrey A. Reimer
, Omar M. Yaghi^*

^*Corresponding author for this work

King Fahd University of Petroleum & Minerals

Research output: Contribution to journal › Article › peer-review

487 Scopus citations

Abstract

The imine linkages of two layered, porous covalent organic frameworks (COFs), TPB-TP-COF ([C₆H₃(C₆H₄N)₃]₂[C₆H₄(CH)₂]₃, 1) and 4PE-1P-COF ([C₂(C₆H₄N)₄][C₆H₄(CH)₂]₂, 2), have been transformed into amide linkages to make the respective isostructural amide COFs 1′ and 2′ by direct oxidation with retention of crystallinity and permanent porosity. Remarkably, the oxidation of both imine COFs is complete, as assessed by FT-IR and ¹³C CP-MAS NMR spectroscopy and demonstrates (a) the first chemical conversion of a COF linkage and (b) how the usual “crystallization problem” encountered in COF chemistry can be bypassed to access COFs, such as these amides, that are typically thought to be difficult to obtain by the usual de novo methods. The amide COFs show improved chemical stability relative to their imine progenitors.

Original language	English
Pages (from-to)	15519-15522
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	48
DOIs	https://doi.org/10.1021/jacs.6b08377
State	Published - 7 Dec 2016

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.6b08377

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@article{d8c42f2ac0fb42739dedc936fe023424,

title = "Chemical Conversion of Linkages in Covalent Organic Frameworks",

abstract = "The imine linkages of two layered, porous covalent organic frameworks (COFs), TPB-TP-COF ([C6H3(C6H4N)3]2[C6H4(CH)2]3, 1) and 4PE-1P-COF ([C2(C6H4N)4][C6H4(CH)2]2, 2), have been transformed into amide linkages to make the respective isostructural amide COFs 1′ and 2′ by direct oxidation with retention of crystallinity and permanent porosity. Remarkably, the oxidation of both imine COFs is complete, as assessed by FT-IR and 13C CP-MAS NMR spectroscopy and demonstrates (a) the first chemical conversion of a COF linkage and (b) how the usual “crystallization problem” encountered in COF chemistry can be bypassed to access COFs, such as these amides, that are typically thought to be difficult to obtain by the usual de novo methods. The amide COFs show improved chemical stability relative to their imine progenitors.",

author = "Waller, \{Peter J.\} and Lyle, \{Steven J.\} and \{Osborn Popp\}, \{Thomas M.\} and Diercks, \{Christian S.\} and Reimer, \{Jeffrey A.\} and Yaghi, \{Omar M.\}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = dec,

day = "7",

doi = "10.1021/jacs.6b08377",

language = "English",

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AU - Waller, Peter J.

AU - Lyle, Steven J.

AU - Osborn Popp, Thomas M.

AU - Diercks, Christian S.

AU - Reimer, Jeffrey A.

AU - Yaghi, Omar M.

PY - 2016/12/7

Y1 - 2016/12/7

N2 - The imine linkages of two layered, porous covalent organic frameworks (COFs), TPB-TP-COF ([C6H3(C6H4N)3]2[C6H4(CH)2]3, 1) and 4PE-1P-COF ([C2(C6H4N)4][C6H4(CH)2]2, 2), have been transformed into amide linkages to make the respective isostructural amide COFs 1′ and 2′ by direct oxidation with retention of crystallinity and permanent porosity. Remarkably, the oxidation of both imine COFs is complete, as assessed by FT-IR and 13C CP-MAS NMR spectroscopy and demonstrates (a) the first chemical conversion of a COF linkage and (b) how the usual “crystallization problem” encountered in COF chemistry can be bypassed to access COFs, such as these amides, that are typically thought to be difficult to obtain by the usual de novo methods. The amide COFs show improved chemical stability relative to their imine progenitors.

AB - The imine linkages of two layered, porous covalent organic frameworks (COFs), TPB-TP-COF ([C6H3(C6H4N)3]2[C6H4(CH)2]3, 1) and 4PE-1P-COF ([C2(C6H4N)4][C6H4(CH)2]2, 2), have been transformed into amide linkages to make the respective isostructural amide COFs 1′ and 2′ by direct oxidation with retention of crystallinity and permanent porosity. Remarkably, the oxidation of both imine COFs is complete, as assessed by FT-IR and 13C CP-MAS NMR spectroscopy and demonstrates (a) the first chemical conversion of a COF linkage and (b) how the usual “crystallization problem” encountered in COF chemistry can be bypassed to access COFs, such as these amides, that are typically thought to be difficult to obtain by the usual de novo methods. The amide COFs show improved chemical stability relative to their imine progenitors.

UR - https://www.scopus.com/pages/publications/85002939083

U2 - 10.1021/jacs.6b08377

DO - 10.1021/jacs.6b08377

M3 - Article

AN - SCOPUS:85002939083

SN - 0002-7863

VL - 138

SP - 15519

EP - 15522

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 48

ER -

Chemical Conversion of Linkages in Covalent Organic Frameworks

Abstract

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ASJC Scopus subject areas

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