Synthesis of Vinylene‐Linked Thiopyrylium‐, Pyrylium‐, and Pyridinium‐Based Covalent Organic Frameworks by Acid‐Catalyzed Aldol Condensation

Ji, Hai‐Feng; Yan, Guoying; Zou, Peng; Wang, Han; Li, Mengke; Feng, Yi; Qu, Xiongwei; Geng, Dongling; Shi, Jingjing; Zhang, Xiaojie

doi:10.1002/chem.202202787

Cited by 9 publications

(10 citation statements)

References 63 publications

(49 reference statements)

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“…Domino reactions were also used to synthesize COFs containing heterocyclium moieties. In 2022, Zhang et al combined heterocyclium transformation and aldol condensation reactions to synthesize thiopyrylium- and pyridinium-based COFs from 2,4,6-trimethylpyrylium tetrafluoroborate (Figure C) . In DMF solution, the 2,4,6-trimethylpyrylium cation was first converted to 2,4,6-trimethylthiopyrylium by a reaction with Na 2 S catalyzed by CF 3 SO 3 H, and the subsequent aldol condensation with aromatic aldehydes at 120 °C afforded Py-COFS n ( n = 1, 2).…”

Section: Mcrs Used For Cof Synthesismentioning

confidence: 99%

Construction of Covalent Organic Frameworks via Multicomponent Reactions

Zhou

Dong

2023

J. Am. Chem. Soc.

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Multicomponent reactions (MCRs) combine at least three reactants to afford the desired product in a highly atomeconomic way and are therefore viewed as efficient one-pot combinatorial synthesis tools allowing one to significantly boost molecular complexity and diversity. Nowadays, MCRs are no longer confined to organic synthesis and have found applications in materials chemistry. In particular, MCRs can be used to prepare covalent organic frameworks (COFs), which are crystalline porous materials assembled from organic monomers and exhibit a broad range of properties and applications. This synthetic approach retains the advantages of small-molecule MCRs, not only strengthening the skeletal robustness of COFs, but also providing additional driving forces for their crystallization, and has been used to prepare a series of robust COFs with diverse applications. The present perspective article provides the general background for MCRs, discusses the types of MCRs employed for COF synthesis to date, and addresses the related critical challenges and future perspectives to inspire the MCR-based design of new robust COFs and promote further progress in this emerging field.

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Section: Mcrs Used For Cof Synthesismentioning

confidence: 99%

Construction of Covalent Organic Frameworks via Multicomponent Reactions

Zhou

Dong

2023

J. Am. Chem. Soc.

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“…However, the stacking energy exhibits that the staggered (ABC) stacking model is more stable (Figure S15), in which the sulfonic-pyridinium zwitterionic pair was oriented to different directions with a 120°angle between the adjacent COF layers to avoid zwitterionic pairs directly on top of each other (Figures 2b and S16). 35,36 Similarly, the PXRD pattern of Zi-VCOF-2 exhibits two distinguishable diffraction peaks at 2θ = 5.9°and 9.9°and several weak peaks at higher angles, demonstrating its crystallinity (Figure 2d). The simulated PXRD pattern and stacking energy also indicated that Zi-VCOF-2 is the staggered (ABC) stacking configuration (Figures 2d,e, S17−S19, and Table S3).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…1700 cm −1 ) of the aldehyde monomers disappeared in COF samples, indicating the high polymerization degrees of Zi-VCOFs. 35,36 The emergence of two new signals at ca. 1610 and 966 cm −1 were attributed to the stretching and bending vibrations of the trans-vinylene bond, confirming the presence of the vinylene linkages in the as-prepared Zi-VCOFs.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The zeta potentials of Zi-VCOF-1 and Zi-VCOF-2 were −5.9 and −12.8 mV, respectively, which were different from those for the reported neutral and cationic vinylene-linked COFs. 35,36,40 Scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HR-TEM) were further conducted to assess the microstructures of Zi-VCOFs. Both Zi-VCOFs exhibit micrometer-sized particles in the SEM images (Figures S25 and S26a,b).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Zwitterionic and Hydrophilic Vinylene-Linked Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Evolution

Ji,

Qiao,

Yan

et al. 2023

ACS Appl. Mater. Interfaces

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Developing effective synthetic strategies as well as broadening functionalities for zwitterionic materials that comprise moieties with equimolar cationic and anionic groups still remains a huge challenge. Herein, we develop two zwitterionic vinylenelinked covalent organic frameworks (Zi-VCOF-1 and Zi-VCOF-2) that are a type of novel hydrophilic material. Zi-VCOF-1 and Zi-VCOF-2 are obtained directly through the convenient Knoevenagel condensation of new sulfonic-pyridinium zwitterionic monomers with aromatic aldehyde derivatives. This is the first report on zwitterionic COFs being constructed by the bottom-up functionalization approach from predesigned zwitterionic monomers. Both Zi-VCOFs exhibit a high photocatalytic hydrogen evolution rate (HER) because of their appropriate optical property and outstanding hydrophilicity. Specifically, Zi-VCOF-1 and Zi-VCOF-2 show photocatalytic HER of 13,547 and 5057 μmol h −1 g −1 , respectively. Interestingly, the photocatalytic HER of Zi-VCOF-1 is about 2.68 times of that of Zi-VCOF-2, although they differ by only one methyl group in sulfonic-pyridinium zwitterionic pairs. The photocatalytic HER of Zi-VCOF-1 is not only the highest in the vinylene-linked COFs but also outstanding among the most reported COFs. This is the first application of zwitterionic COFs for photocatalytic hydrogen evolution, which would open a new frontier in zwitterionic COFs and be helpful for the design of other photocatalytic materials.

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“…Aldol condensation combines two carbonyl compounds (at least one has an α-carbon atom) to form a new β-hydroxy carbonyl compound under the catalysis of protonic acid, which undergoes dehydration to form a vinylene bond. 43,44 In 2019, Yaghi developed an olefin-linked COF (COF-701) via trifluoroacetic acid-catalyzed aldol condensation between 2,4,6-trimethyl-1,3,5-triazine (TMT) and 4,4′-biphenyldicarbaldehyde (BPDA). 45 The crystallinity of COF-701 with a staggered (AB) stacking mode was confirmed by wide-angle X-ray scattering.…”

Section: Reaction In CC Linked Cofsmentioning

confidence: 99%