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Title: Formation Mechanisms and Defect Engineering of Imine-Based Porous Organic Cages

Abstract

The 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 find 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. Based on 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 to design intentionally defective cages. These “missing-linker” type molecular defects are installed into CC3-R via non-solvent induced crystallization. The defective CC3-R materials are found to have enhanced CO2 interaction and improved CO 2 uptake capacity due to the additional functional groups present within the CC3 crystals.

Authors:
 [1];  [1];  [2];  [2];  [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States)
  2. Univ. of Alabama, Tuscaloosa, AL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470285
Grant/Contract Number:  
SC0012577
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 1; Related Information: UNCAGE-ME partners with Georgia Institute of Technology (lead); Lehigh University; Oak Ridge National Laboratory; University of Alabama; University of Florida; University of Wisconsin; Washington University in St. Louis; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); defects; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

Zhu, Guanghui, Liu, Yang, Flores, Luis, Lee, Zachary R., Jones, Christopher W., Dixon, David A., Sholl, David S., and Lively, Ryan P. Formation Mechanisms and Defect Engineering of Imine-Based Porous Organic Cages. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b04323.
Zhu, Guanghui, Liu, Yang, Flores, Luis, Lee, Zachary R., Jones, Christopher W., Dixon, David A., Sholl, David S., & Lively, Ryan P. Formation Mechanisms and Defect Engineering of Imine-Based Porous Organic Cages. United States. doi:10.1021/acs.chemmater.7b04323.
Zhu, Guanghui, Liu, Yang, Flores, Luis, Lee, Zachary R., Jones, Christopher W., Dixon, David A., Sholl, David S., and Lively, Ryan P. Mon . "Formation Mechanisms and Defect Engineering of Imine-Based Porous Organic Cages". United States. doi:10.1021/acs.chemmater.7b04323. https://www.osti.gov/servlets/purl/1470285.
@article{osti_1470285,
title = {Formation Mechanisms and Defect Engineering of Imine-Based Porous Organic Cages},
author = {Zhu, Guanghui and Liu, Yang and Flores, Luis and Lee, Zachary R. and Jones, Christopher W. and Dixon, David A. and Sholl, David S. and Lively, Ryan P.},
abstractNote = {The 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 find 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. Based on 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 to design intentionally defective cages. These “missing-linker” type molecular defects are installed into CC3-R via non-solvent induced crystallization. The defective CC3-R materials are found to have enhanced CO2 interaction and improved CO2 uptake capacity due to the additional functional groups present within the CC3 crystals.},
doi = {10.1021/acs.chemmater.7b04323},
journal = {Chemistry of Materials},
number = 1,
volume = 30,
place = {United States},
year = {2017},
month = {12}
}

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Works referencing / citing this record:

High-throughput discovery of organic cages and catenanes using computational screening fused with robotic synthesis
journal, July 2018


Dynamic polyimine macrobicyclic cryptands – self-sorting with component selection
journal, January 2019

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