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Issue 30, 2018
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Mechanistic investigations into the cyclization and crystallization of benzobisoxazole-linked two-dimensional covalent organic frameworks

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Abstract

Although many diverse covalent organic frameworks (COFs) have been synthesised over the past decade, our fundamental understanding of their nucleation and growth during the crystallization process has progressed slowly for many systems. In this work, we report the first in-depth mechanistic investigation detailing the role of nucleophilic catalysts during the formation of two distinct benzobisoxazole (BBO)-linked COFs. The BBO-COFs were constructed by reacting 1,3,5-tris(4-formylphenyl)benzene (TFPB) and 1,3,5-tris(4-formylphenyl)triazine (TFPT) C3-symmetric monomers with a C2-symmetric o-aminophenol substituted precursor using different nucleophiles (e.g. NaCN, NaN3, and NaSCH3). Our experimental and computational results demonstrate that the nucleophiles help initiate an oxidative dehydrogenation pathway by producing radical intermediates that are stabilized by a captodative effect. We also demonstrate that the electron deficient TFPT monomer not only aids in enhancing the crystallinity of the BBO-COFs but also participates in the delocalization of the radicals generated to help stabilize the intermediates.

Graphical abstract: Mechanistic investigations into the cyclization and crystallization of benzobisoxazole-linked two-dimensional covalent organic frameworks

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Publication details

The article was received on 13 Apr 2018, accepted on 22 Jun 2018 and first published on 25 Jun 2018


Article type: Edge Article
DOI: 10.1039/C8SC01683F
Citation: Chem. Sci., 2018,9, 6417-6423
  • Open access: Creative Commons BY license
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    Mechanistic investigations into the cyclization and crystallization of benzobisoxazole-linked two-dimensional covalent organic frameworks

    D. A. Pyles, W. H. Coldren, Grace M. Eder, C. M. Hadad and P. L. McGrier, Chem. Sci., 2018, 9, 6417
    DOI: 10.1039/C8SC01683F

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