| Autor: |
Pyles DA; Department of Chemistry & Biochemistry , The Ohio State University , Columbus , Ohio 43210 , USA., Coldren WH; Department of Chemistry & Biochemistry , The Ohio State University , Columbus , Ohio 43210 , USA., Eder GM; Department of Chemistry & Biochemistry , The Ohio State University , Columbus , Ohio 43210 , USA., Hadad CM; Department of Chemistry & Biochemistry , The Ohio State University , Columbus , Ohio 43210 , USA., McGrier PL; Department of Chemistry & Biochemistry , The Ohio State University , Columbus , Ohio 43210 , USA. |
| Abstrakt: |
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) C 3 -symmetric monomers with a C 2 -symmetric o -aminophenol substituted precursor using different nucleophiles ( e.g. NaCN, NaN 3 , and NaSCH 3 ). 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. |
