Formation Mechanisms and Defect Engineering of Imine-Based Porous Organic Cages
| Autor: | David A. Dixon, David S. Sholl, Luis A. Flores, Ryan P. Lively, Yang Liu, Guanghui Zhu, Zachary R. Lee, Christopher W. Jones |
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| Rok vydání: | 2017 |
| Předmět: |
Reaction mechanism
010405 organic chemistry General Chemical Engineering Imine Rational design Dynamic covalent chemistry Molecular orbital theory General Chemistry Electronic structure 010402 general chemistry 01 natural sciences 0104 chemical sciences chemistry.chemical_compound chemistry Computational chemistry Materials Chemistry Density functional theory Porosity |
| Zdroj: | Chemistry of Materials. 30:262-272 |
| ISSN: | 1520-5002 0897-4756 |
| DOI: | 10.1021/acs.chemmater.7b04323 |
| Popis: | Syntheses of porous organic cages (POCs) represent an important synthetic puzzle in dynamic covalent chemistry-based self-sorting. Improved understanding of the formation mechanisms of POCs can lead to control and rational design of cages with desired functionality. Herein, we explore the formation mechanisms of imine-based POCs using time-resolved electrospray mass spectrometry and electronic structure calculations at the density functional theory and correlated molecular orbital theory levels. We found that the synthesis of the [4 + 6] cycloimine cage CC3-R and the [2 + 3] cycloimine cage CC-pentane both proceed through similar intermediates via a series of consecutive reactions. The proposed reaction mechanisms are supported by electronic structure calculations. On the basis of our observations from both experiments and calculations, we propose a comprehensive method for designing and predicting new POC species. In addition, the observation of stable incomplete cages during CC3-R synthesis inspired us ... |
| Databáze: | OpenAIRE |
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