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Hydrolytic Stability of Boronate Ester‐Linked Covalent Organic Frameworks
Author(s) -
Li Huifang,
Li Haoyuan,
Dai Qingqing,
Li Hong,
Brédas JeanLuc
Publication year - 2018
Publication title -
advanced theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.068
H-Index - 17
ISSN - 2513-0390
DOI - 10.1002/adts.201700015
Subject(s) - chemistry , hydrolysis , covalent bond , molecule , nucleophile , monomer , bond dissociation energy , dissociation (chemistry) , chemical stability , organic chemistry , combinatorial chemistry , computational chemistry , polymer chemistry , catalysis , polymer
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 2 O molecule, has a relatively high energy barrier of 22.3 kcal mol −1 . However, the presence of an additional H 2 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.