Hydrolytic Stability of Boronate Ester-Linked Covalent Organic Frameworks

Handle URI:
http://hdl.handle.net/10754/627259
Title:
Hydrolytic Stability of Boronate Ester-Linked Covalent Organic Frameworks
Authors:
Li, Huifang; Li, Haoyuan ( 0000-0002-2469-5842 ) ; Dai, Qingqing; Li, Hong; Bredas, Jean-Luc ( 0000-0001-7278-4471 )
Abstract:
The stability of covalent organic frameworks (COFs) is essential to their applications. However, the common boronate ester-linked COFs are susceptible to attack by nucleophiles (such as water molecules) at the electron-deficient boron sites. To provide an understanding of the hydrolytic stability of the representative boronate ester-linked COF-5 and of the associated hydrolysis mechanisms, density functional theory (DFT) calculations were performed to characterize the hydrolysis reactions of the molecule formed by the condensation of 1,4-phenylenebis(boronic acid) (PBBA) and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) monomers; two cases were considered, one dealing with the freestanding molecule and the other with the molecule interacting with COF layers. It was found that the boronate ester (B–O) bond dissociation, which requires one H2O molecule, has a relatively high energy barrier of 22.3 kcal mol−1. However, the presence of an additional H2O molecule significantly accelerates hydrolysis by reducing the energy barrier by a factor of 3. Importantly, the hydrolysis of boronate ester bonds situated in a COF environment follows reaction pathways that are different and have increased energy barriers. These results point to an enhanced hydrolytic stability of COF-5 crystals.
KAUST Department:
KAUST Solar Center (KSC); Physical Sciences and Engineering (PSE) Division; Laboratory for Computational and Theoretical Chemistry of Advanced Materials
Citation:
Li H, Li H, Dai Q, Li H, Brédas J-L (2018) Hydrolytic Stability of Boronate Ester-Linked Covalent Organic Frameworks. Advanced Theory and Simulations 1: 1700015. Available: http://dx.doi.org/10.1002/adts.201700015.
Publisher:
Wiley-Blackwell
Journal:
Advanced Theory and Simulations
Issue Date:
30-Jan-2018
DOI:
10.1002/adts.201700015
Type:
Article
ISSN:
2513-0390
Sponsors:
Army Research Office[W911NF-15-1-0447, W911NF-17-1-0339]; King Abdullah University of Science and Technology; National Natural Science Foundation of China[21403037]
Additional Links:
onlinelibrary.wiley.com/doi/10.1002/adts.201700015/abstract
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Solar Center (KSC)

Full metadata record

DC FieldValue Language
dc.contributor.authorLi, Huifangen
dc.contributor.authorLi, Haoyuanen
dc.contributor.authorDai, Qingqingen
dc.contributor.authorLi, Hongen
dc.contributor.authorBredas, Jean-Lucen
dc.date.accessioned2018-03-11T06:54:12Z-
dc.date.available2018-03-11T06:54:12Z-
dc.date.issued2018-01-30en
dc.identifier.citationLi H, Li H, Dai Q, Li H, Brédas J-L (2018) Hydrolytic Stability of Boronate Ester-Linked Covalent Organic Frameworks. Advanced Theory and Simulations 1: 1700015. Available: http://dx.doi.org/10.1002/adts.201700015.en
dc.identifier.issn2513-0390en
dc.identifier.doi10.1002/adts.201700015en
dc.identifier.urihttp://hdl.handle.net/10754/627259-
dc.description.abstractThe stability of covalent organic frameworks (COFs) is essential to their applications. However, the common boronate ester-linked COFs are susceptible to attack by nucleophiles (such as water molecules) at the electron-deficient boron sites. To provide an understanding of the hydrolytic stability of the representative boronate ester-linked COF-5 and of the associated hydrolysis mechanisms, density functional theory (DFT) calculations were performed to characterize the hydrolysis reactions of the molecule formed by the condensation of 1,4-phenylenebis(boronic acid) (PBBA) and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) monomers; two cases were considered, one dealing with the freestanding molecule and the other with the molecule interacting with COF layers. It was found that the boronate ester (B–O) bond dissociation, which requires one H2O molecule, has a relatively high energy barrier of 22.3 kcal mol−1. However, the presence of an additional H2O molecule significantly accelerates hydrolysis by reducing the energy barrier by a factor of 3. Importantly, the hydrolysis of boronate ester bonds situated in a COF environment follows reaction pathways that are different and have increased energy barriers. These results point to an enhanced hydrolytic stability of COF-5 crystals.en
dc.description.sponsorshipArmy Research Office[W911NF-15-1-0447, W911NF-17-1-0339]en
dc.description.sponsorshipKing Abdullah University of Science and Technologyen
dc.description.sponsorshipNational Natural Science Foundation of China[21403037]en
dc.publisherWiley-Blackwellen
dc.relation.urlonlinelibrary.wiley.com/doi/10.1002/adts.201700015/abstracten
dc.titleHydrolytic Stability of Boronate Ester-Linked Covalent Organic Frameworksen
dc.typeArticleen
dc.contributor.departmentKAUST Solar Center (KSC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentLaboratory for Computational and Theoretical Chemistry of Advanced Materialsen
dc.identifier.journalAdvanced Theory and Simulationsen
dc.contributor.institutionSchool of Chemistry and Biochemistry; Center for Organic Photonics and Electronics; Georgia Institute of Technology; Atlanta GA 30332-0400 USAen
kaust.authorLi, Huifangen
kaust.authorBredas, Jean-Lucen
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