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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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Supplementary files

Article information


Submitted
13 Apr 2018
Accepted
22 Jun 2018
First published
25 Jun 2018

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2018,9, 6417-6423
Article type
Edge Article

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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