Hydrolytic Stability of Boronate Ester‐Linked Covalent Organic Frameworks

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  • Huifang Li
    Laboratory for Computational and Theoretical Chemistry of Advanced Materials Physical Science and Engineering Division King Abdullah University of Science and Technology Thuwal 23955–6900 Kingdom of Saudi Arabia
  • Haoyuan Li
    School of Chemistry and Biochemistry Center for Organic Photonics and Electronics Georgia Institute of Technology Atlanta GA 30332–0400 USA
  • Qingqing Dai
    School of Chemistry and Biochemistry Center for Organic Photonics and Electronics Georgia Institute of Technology Atlanta GA 30332–0400 USA
  • Hong Li
    School of Chemistry and Biochemistry Center for Organic Photonics and Electronics Georgia Institute of Technology Atlanta GA 30332–0400 USA
  • Jean‐Luc Brédas
    Laboratory for Computational and Theoretical Chemistry of Advanced Materials Physical Science and Engineering Division King Abdullah University of Science and Technology Thuwal 23955–6900 Kingdom of Saudi Arabia

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<jats:title>Abstract</jats:title><jats:p>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 H<jats:sub>2</jats:sub>O molecule, has a relatively high energy barrier of 22.3 kcal mol<jats:sup>−1</jats:sup>. However, the presence of an additional H<jats:sub>2</jats:sub>O 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.</jats:p>

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