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 CO2 uptake capacity due to the additional functional groups present within the CC3 crystals.
- Authors:
-
- Georgia Inst. of Technology, Atlanta, GA (United States)
- 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)
- 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. https://doi.org/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. https://doi.org/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 = {Mon Dec 11 00:00:00 EST 2017},
month = {Mon Dec 11 00:00:00 EST 2017}
}
Web of Science
Works referenced in this record:
Porous organic cages
journal, October 2009
- Tozawa, Tomokazu; Jones, James T. A.; Swamy, Shashikala I.
- Nature Materials, Vol. 8, Issue 12, p. 973-978
Porous organic molecules
journal, October 2010
- Holst, James R.; Trewin, Abbie; Cooper, Andrew I.
- Nature Chemistry, Vol. 2, Issue 11
Modular and predictable assembly of porous organic molecular crystals
journal, June 2011
- Jones, James T. A.; Hasell, Tom; Wu, Xiaofeng
- Nature, Vol. 474, Issue 7351
Molecular Organic Crystals: From Barely Porous to Really Porous
journal, June 2012
- Cooper, Andrew I.
- Angewandte Chemie International Edition, Vol. 51, Issue 32
One-pot synthesis of a shape-persistent endo-functionalised nano-sized adamantoid compound
journal, January 2008
- Mastalerz, Michael
- Chemical Communications, Issue 39
Shape-Persistent Organic Cage Compounds by Dynamic Covalent Bond Formation
journal, June 2010
- Mastalerz, Michael
- Angewandte Chemie International Edition, Vol. 49, Issue 30
A Salicylbisimine Cage Compound with High Surface Area and Selective CO2/CH4 Adsorption
journal, November 2010
- Mastalerz, Michael; Schneider, Markus W.; Oppel, Iris M.
- Angewandte Chemie International Edition, Vol. 50, Issue 5, p. 1046-1051
Permanent Porous Materials from Discrete Organic Molecules-Towards Ultra-High Surface Areas
journal, July 2012
- Mastalerz, Michael
- Chemistry - A European Journal, Vol. 18, Issue 33
A Permanent Mesoporous Organic Cage with an Exceptionally High Surface Area
journal, January 2014
- Zhang, Gang; Presly, Oliver; White, Fraser
- Angewandte Chemie International Edition, Vol. 53, Issue 6
Development of organic porous materials through Schiff-base chemistry
journal, January 2013
- Jin, Yinghua; Zhu, Youlong; Zhang, Wei
- CrystEngComm, Vol. 15, Issue 8
Design Strategies for Shape-Persistent Covalent Organic Polyhedrons (COPs) through Imine Condensation/Metathesis
journal, August 2012
- Jin, Yinghua; Jin, Athena; McCaffrey, Ryan
- The Journal of Organic Chemistry, Vol. 77, Issue 17
Porous organic cages: soluble, modular and molecular pores
journal, July 2016
- Hasell, Tom; Cooper, Andrew I.
- Nature Reviews Materials, Vol. 1, Issue 9
Synthesis and Applications of Porous Organic Cages
journal, May 2015
- Evans, Jack D.; Sumby, Christopher J.; Doonan, Christian J.
- Chemistry Letters, Vol. 44, Issue 5
Porous Molecular Solids and Liquids
journal, May 2017
- Cooper, Andrew I.
- ACS Central Science, Vol. 3, Issue 6
Organic cage compounds – from shape-persistency to function
journal, January 2014
- Zhang, Gang; Mastalerz, Michael
- Chem. Soc. Rev., Vol. 43, Issue 6
Toward Homogenization of Heterogeneous Metal Nanoparticle Catalysts with Enhanced Catalytic Performance: Soluble Porous Organic Cage as a Stabilizer and Homogenizer
journal, June 2015
- Sun, Jian-Ke; Zhan, Wen-Wen; Akita, Tomoki
- Journal of the American Chemical Society, Vol. 137, Issue 22
Porous Organic Cage Thin Films and Molecular-Sieving Membranes
journal, January 2016
- Song, Qilei; Jiang, Shan; Hasell, Tom
- Advanced Materials, Vol. 28, Issue 13
Radical Polymerization of Vinyl Monomers in Porous Organic Cages
journal, March 2016
- Uemura, Takashi; Nakanishi, Ryo; Mochizuki, Shuto
- Angewandte Chemie International Edition, Vol. 55, Issue 22
A chiral porous organic cage for molecular recognition using gas chromatography
journal, January 2016
- Xie, Sheng-Ming; Zhang, Jun-Hui; Fu, Nan
- Analytica Chimica Acta, Vol. 903
Amine Molecular Cages as Supramolecular Fluorescent Explosive Sensors: A Computational Perspective
journal, May 2016
- Zwijnenburg, Martijn A.; Berardo, Enrico; Peveler, William J.
- The Journal of Physical Chemistry B, Vol. 120, Issue 22
Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C 70 -Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium
journal, March 2017
- Ortiz, Michael; Cho, Sung; Niklas, Jens
- Journal of the American Chemical Society, Vol. 139, Issue 12
Mixed-Matrix Membranes
journal, July 2017
- Dechnik, Janina; Gascon, Jorge; Doonan, Christian J.
- Angewandte Chemie International Edition, Vol. 56, Issue 32
Microporous Organic Materials for Membrane-Based Gas Separation
journal, October 2017
- Zou, Xiaoqin; Zhu, Guangshan
- Advanced Materials, Vol. 30, Issue 3
In silico Design of Supramolecules from Their Precursors: Odd–Even Effects in Cage-Forming Reactions
journal, June 2013
- Jelfs, Kim E.; Eden, Edward G. B.; Culshaw, Jamie L.
- Journal of the American Chemical Society, Vol. 135, Issue 25
A Perspective on the Synthesis, Purification, and Characterization of Porous Organic Cages
journal, September 2016
- Briggs, Michael E.; Cooper, Andrew I.
- Chemistry of Materials, Vol. 29, Issue 1
Application of computational methods to the design and characterisation of porous molecular materials
journal, January 2017
- Evans, Jack D.; Jelfs, Kim E.; Day, Graeme M.
- Chemical Society Reviews, Vol. 46, Issue 11
Reticular synthesis of porous molecular 1D nanotubes and 3D networks
journal, November 2016
- Slater, A. G.; Little, M. A.; Pulido, A.
- Nature Chemistry, Vol. 9, Issue 1
Functional materials discovery using energy–structure–function maps
journal, March 2017
- Pulido, Angeles; Chen, Linjiang; Kaczorowski, Tomasz
- Nature, Vol. 543, Issue 7647
Dynamic Covalent Chemistry Approaches Toward Macrocycles, Molecular Cages, and Polymers
journal, April 2014
- Jin, Yinghua; Wang, Qi; Taynton, Philip
- Accounts of Chemical Research, Vol. 47, Issue 5
Nanoporous Organics Enter the Cage Age
journal, December 2010
- Cooper, Andrew I.
- Angewandte Chemie International Edition, Vol. 50, Issue 5
Selective gas sorption in a [2+3] ‘propeller’ cage crystal
journal, January 2011
- Jiang, Shan; Bacsa, John; Wu, Xiaofeng
- Chemical Communications, Vol. 47, Issue 31
Large Self-Assembled Chiral Organic Cages: Synthesis, Structure, and Shape Persistence
journal, September 2011
- Jelfs, Kim E.; Wu, Xiaofeng; Schmidtmann, Marc
- Angewandte Chemie International Edition, Vol. 50, Issue 45
Topological landscapes of porous organic cages
journal, January 2017
- Santolini, Valentina; Miklitz, Marcin; Berardo, Enrico
- Nanoscale, Vol. 9, Issue 16
Porous organic molecular solids by dynamic covalent scrambling
journal, February 2011
- Jiang, Shan; Jones, James T. A.; Hasell, Tom
- Nature Communications, Vol. 2, Issue 1
Dynamic flow synthesis of porous organic cages
journal, January 2015
- Briggs, Michael E.; Slater, Anna G.; Lunt, Neil
- Chemical Communications, Vol. 51, Issue 98
Dynamic imine chemistry
journal, January 2012
- Belowich, Matthew E.; Stoddart, J. Fraser
- Chemical Society Reviews, Vol. 41, Issue 6
Kinetically Trapped Tetrahedral Cages via Alkyne Metathesis
journal, February 2016
- Lee, Semin; Yang, Anna; Moneypenny, Timothy P.
- Journal of the American Chemical Society, Vol. 138, Issue 7
Solvent Effects in Thermodynamically Controlled Multicomponent Nanocage Syntheses
journal, November 2006
- Liu, Xuejun; Warmuth, Ralf
- Journal of the American Chemical Society, Vol. 128, Issue 43
Interferences and contaminants encountered in modern mass spectrometry
journal, October 2008
- Keller, Bernd O.; Sui, Jie; Young, Alex B.
- Analytica Chimica Acta, Vol. 627, Issue 1
MP2 energy evaluation by direct methods
journal, December 1988
- Head-Gordon, Martin; Pople, John A.; Frisch, Michael J.
- Chemical Physics Letters, Vol. 153, Issue 6
Theoretical models incorporating electron correlation
journal, January 1976
- Pople, John A.; Binkley, J. Stephen; Seeger, Rolf
- International Journal of Quantum Chemistry, Vol. 10, Issue S10
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992
- Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
- The Journal of Chemical Physics, Vol. 96, Issue 9
Note on an Approximation Treatment for Many-Electron Systems
journal, October 1934
- Møller, Chr.; Plesset, M. S.
- Physical Review, Vol. 46, Issue 7
Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
- Becke, Axel D.
- The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988
- Lee, Chengteh; Yang, Weitao; Parr, Robert G.
- Physical Review B, Vol. 37, Issue 2
Optimization of Gaussian-type basis sets for local spin density functional calculations. Part I. Boron through neon, optimization technique and validation
journal, February 1992
- Godbout, Nathalie; Salahub, Dennis R.; Andzelm, Jan
- Canadian Journal of Chemistry, Vol. 70, Issue 2
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
journal, January 2008
- Chai, Jeng-Da; Head-Gordon, Martin
- Physical Chemistry Chemical Physics, Vol. 10, Issue 44
A Density Functional with Spherical Atom Dispersion Terms
journal, September 2012
- Austin, Amy; Petersson, George A.; Frisch, Michael J.
- Journal of Chemical Theory and Computation, Vol. 8, Issue 12
MN15: A Kohn–Sham global-hybrid exchange–correlation density functional with broad accuracy for multi-reference and single-reference systems and noncovalent interactions
journal, January 2016
- Yu, Haoyu S.; He, Xiao; Li, Shaohong L.
- Chemical Science, Vol. 7, Issue 8
Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects
journal, February 1981
- Miertuš, S.; Scrocco, E.; Tomasi, J.
- Chemical Physics, Vol. 55, Issue 1
COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient
journal, January 1993
- Klamt, A.; Schüürmann, G.
- J. Chem. Soc., Perkin Trans. 2, Issue 5
β-Ketoenamine-Linked Covalent Organic Frameworks Capable of Pseudocapacitive Energy Storage
journal, October 2013
- DeBlase, Catherine R.; Silberstein, Katharine E.; Truong, Thanh-Tam
- Journal of the American Chemical Society, Vol. 135, Issue 45
Construction of Crystalline 2D Covalent Organic Frameworks with Remarkable Chemical (Acid/Base) Stability via a Combined Reversible and Irreversible Route
journal, November 2012
- Kandambeth, Sharath; Mallick, Arijit; Lukose, Binit
- Journal of the American Chemical Society, Vol. 134, Issue 48
Chiral 2 + 3 Keto-Enamine Pseudocyclophanes Derived from 1,3,5-Triformylphloroglucinol
journal, December 2015
- Kieryk, Przemysław; Janczak, Jan; Panek, Jarosław
- Organic Letters, Vol. 18, Issue 1
Chiral, triformylphenol-derived salen-type [4 + 6] organic cages
journal, January 2016
- Petryk, M.; Szymkowiak, J.; Gierczyk, B.
- Organic & Biomolecular Chemistry, Vol. 14, Issue 31
Odd-Even Alternation in Tautomeric Porous Organic Cages with Exceptional Chemical Stability
journal, January 2017
- Bera, Saibal; Basu, Arghya; Tothadi, Srinu
- Angewandte Chemie International Edition, Vol. 56, Issue 8
Supramolecular Engineering of Intrinsic and Extrinsic Porosity in Covalent Organic Cages
journal, October 2011
- Bojdys, Michael J.; Briggs, Michael E.; Jones, James T. A.
- Journal of the American Chemical Society, Vol. 133, Issue 41
Stereospecific Synthesis of Alkyl-Substituted Vicinal Diamines from the Mother Diamine: Overcoming the “Intrinsic Barrier” to the Diaza-Cope Rearrangement Reaction
journal, December 2008
- Kim, Hyunwoo; Staikova, Mima; Lough, Alan J.
- Organic Letters, Vol. 11, Issue 1
Stereospecific Synthesis of C 2 Symmetric Diamines from the Mother Diamine by Resonance-Assisted Hydrogen-Bond Directed Diaza-Cope Rearrangement
journal, August 2008
- Kim, Hyunwoo; Nguyen, Yen; Yen, Cindy Pai-Hui
- Journal of the American Chemical Society, Vol. 130, Issue 36
Stereospecific Diaza-Cope Rearrangement Driven by Steric Strain
journal, October 2008
- Kim, Hyunwoo; Nguyen, Yen; Lough, Alan J.
- Angewandte Chemie International Edition, Vol. 47, Issue 45
Interplay between defects, disorder and flexibility in metal-organic frameworks
journal, December 2016
- Bennett, Thomas D.; Cheetham, Anthony K.; Fuchs, Alain H.
- Nature Chemistry, Vol. 9, Issue 1
Defects in Metal–Organic Frameworks: Challenge or Opportunity?
journal, August 2015
- Sholl, David S.; Lively, Ryan P.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 17
Defects in metal–organic frameworks: a compromise between adsorption and stability?
journal, January 2016
- Thornton, A. W.; Babarao, R.; Jain, A.
- Dalton Transactions, Vol. 45, Issue 10
Melt-Quenched Glasses of Metal–Organic Frameworks
journal, March 2016
- Bennett, Thomas D.; Yue, Yuanzheng; Li, Peng
- Journal of the American Chemical Society, Vol. 138, Issue 10
Solid Solutions of Soft Porous Coordination Polymers: Fine-Tuning of Gas Adsorption Properties
journal, May 2010
- Fukushima, Tomohiro; Horike, Satoshi; Inubushi, Yasutaka
- Angewandte Chemie, Vol. 122, Issue 28
Engineering Porous Organic Cage Crystals with Increased Acid Gas Resistance
journal, June 2016
- Zhu, Guanghui; Hoffman, Christopher D.; Liu, Yang
- Chemistry - A European Journal, Vol. 22, Issue 31
Computational Characterization of Defects in Metal–Organic Frameworks: Spontaneous and Water-Induced Point Defects in ZIF-8
journal, January 2016
- Zhang, Chenyang; Han, Chu; Sholl, David S.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 3
Defect-Engineered Metal-Organic Frameworks
journal, June 2015
- Fang, Zhenlan; Bueken, Bart; De Vos, Dirk E.
- Angewandte Chemie International Edition, Vol. 54, Issue 25
RASPA: molecular simulation software for adsorption and diffusion in flexible nanoporous materials
journal, February 2015
- Dubbeldam, David; Calero, Sofía; Ellis, Donald E.
- Molecular Simulation, Vol. 42, Issue 2
DREIDING: a generic force field for molecular simulations
journal, December 1990
- Mayo, Stephen L.; Olafson, Barry D.; Goddard, William A.
- The Journal of Physical Chemistry, Vol. 94, Issue 26, p. 8897-8909
Works referencing / citing this record:
Computational discovery of molecular C60 encapsulants with an evolutionary algorithm
journal, January 2020
- Miklitz, Marcin; Turcani, Lukas; Greenaway, Rebecca L.
- Communications Chemistry, Vol. 3, Issue 1
High-throughput discovery of organic cages and catenanes using computational screening fused with robotic synthesis
journal, July 2018
- Greenaway, R. L.; Santolini, V.; Bennison, M. J.
- Nature Communications, Vol. 9, Issue 1
Organic Cage Dumbbells
journal, March 2020
- Greenaway, Rebecca L.; Santolini, Valentina; Szczypiński, Filip T.
- Chemistry – A European Journal, Vol. 26, Issue 17
In silico design and assembly of cage molecules into porous molecular materials
journal, January 2018
- Bernabei, Marco; Pérez-Soto, Raúl; Gómez García, Ismael
- Molecular Systems Design & Engineering, Vol. 3, Issue 6
Dynamic polyimine macrobicyclic cryptands – self-sorting with component selection
journal, January 2019
- Kołodziejski, Michał; Stefankiewicz, Artur R.; Lehn, Jean-Marie
- Chemical Science, Vol. 10, Issue 6
Solvothermal synthesis of porous organic cage CC3 in the presence of dimethylformamide as solvent
journal, January 2019
- Lucero, Jolie; Crawford, James M.; Osuna, Carla
- CrystEngComm, Vol. 21, Issue 34
Computational discovery of a large-imine-cage-based porous molecular material and its application in water desalination
journal, January 2019
- Bernabei, Marco; Pérez Soto, Raul; Gómez García, Ismael
- Molecular Systems Design & Engineering, Vol. 4, Issue 4
From Concept to Crystals via Prediction: Multi‐Component Organic Cage Pots by Social Self‐Sorting
journal, September 2019
- Greenaway, Rebecca L.; Santolini, Valentina; Pulido, Angeles
- Angewandte Chemie, Vol. 131, Issue 45
Computational screening for nested organic cage complexes
journal, January 2020
- Berardo, Enrico; Greenaway, Rebecca L.; Miklitz, Marcin
- Molecular Systems Design & Engineering, Vol. 5, Issue 1