Self‐Assembly of Helical Nanofibrous Chiral Covalent Organic Frameworks

Tang, Xihao; Liao, Xiang‐Ji; Cai, Xinting; Wu, Jialin; Wu, Xueying; Zhang, Qianni; Yan, Yilun; Zheng, Sheng‐Run; Jiang, Huawei; Fan, Jun; Cai, Song‐Liang; Zhang, Weiguang; Liu, Yi

doi:10.1002/anie.202216310

“…In view of its stability, ( S )-DTP-COF could be reused 10 times without observable changes in micromorphology and crystallinity and with only marginal decreases in yield and stereoselectivity. The above study is the first one to show the power of asymmetric MCRs for the synthesis of chiral COFs, providing a fourth new method (catalytic asymmetric polymerization) of synthesizing chiral COFs in addition to direct synthesis, PSM, and chiral induction …”

Section: Mcrs Used For Cof Synthesismentioning

confidence: 94%

Construction of Covalent Organic Frameworks via Multicomponent Reactions

Zhou

¹

,

Dong

²

2023

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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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“…The increase in crosslinking degrees through the breaking and reorganization of imine bonds during the amorphous to crystalline transformation was central to the formation of stable COFs. The solid-state 13 C CP-MAS NMR spectra also showed characteristic peaks for C=N at 157 ppm ((R)-Tf-Pa and (R)-Tf-BD) and 154 ppm ((R)-Tf-BD-Me 2 ), whereas there was almost no characteristic peak for C=O around 190 ppm (Figure 4c). [17a] Thermogravimetric analysis suggested that these helical COPs and COFs had high thermal stabilities, with mass retention of over 90 % at 400 °C (Figure S10).…”

Section: Methodsmentioning

confidence: 99%

Sculpting Mesoscopic Helical Chirality into Covalent Organic Framework Nanotubes from Entirely Achiral Building Blocks

Zha,

Xu,

Khan

et al. 2023

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The diversification of chirality in covalent organic frameworks (COFs) holds immense promise for expanding their properties and functionality. Herein, we introduce an innovative approach for imparting helical chirality to COFs and fabricating a family of chiral COF nanotubes with mesoscopic helicity from entirely achiral building blocks for the first time. We present an effective 2,3‐diaminopyridine‐mediated supramolecular templating method, which facilitates the prefabrication of helical imine‐linked polymer nanotubes using unprecedented achiral symmetric monomers. Through meticulous optimization of crystallization conditions, these helical polymer nanotubes are adeptly converted into imine‐linked COF nanotubes boasting impressive surface areas, while well preserving their helical morphology and chiroptical properties. Furthermore, these helical imine‐linked polymers or COFs could be subtly transformed into corresponding more stable and functional helical β‐ketoenamine‐linked and hydrazone‐linked COF nanotubes with transferred circular dichroism via monomer exchange. Notably, despite the involvement of covalent bonding breakage and reorganization, these exchange processes overcome thermodynamic disadvantages, allowing mesoscopic helical chirality to be perfectly preserved. This research highlights the potential of mesoscopic helicity in conferring COFs with favourable chiral properties, providing novel insights into the development of multifunctional COFs in the field of chiral materials chemistry.

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“…This leads to the resulting products typically characterized by randomly oriented aggregate clusters, posing a challenge in achieving well‐defined mesoscopic helicity within traditional synthetic systems [12] . To the best of our knowledge, only one recent example of single‐handed helical COFs with chiroptical activities has been reported [13] . This noteworthy study demonstrated that molecular chirality in COF could be amplified to helical chirality.…”

Section: Introductionmentioning

confidence: 92%

Sculpting Mesoscopic Helical Chirality into Covalent Organic Framework Nanotubes from Entirely Achiral Building Blocks

Zha,

Xu,

Khan

et al. 2023

Angewandte Chemie

0

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The diversification of chirality in covalent organic frameworks (COFs) holds immense promise for expanding their properties and functionality. Herein, we introduce an innovative approach for imparting helical chirality to COFs and fabricating a family of chiral COF nanotubes with mesoscopic helicity from entirely achiral building blocks for the first time. We present an effective 2,3‐diaminopyridine‐mediated supramolecular templating method, which facilitates the prefabrication of helical imine‐linked polymer nanotubes using unprecedented achiral symmetric monomers. Through meticulous optimization of crystallization conditions, these helical polymer nanotubes are adeptly converted into imine‐linked COF nanotubes boasting impressive surface areas, while well preserving their helical morphology and chiroptical properties. Furthermore, these helical imine‐linked polymers or COFs could be subtly transformed into corresponding more stable and functional helical β‐ketoenamine‐linked and hydrazone‐linked COF nanotubes with transferred circular dichroism via monomer exchange. Notably, despite the involvement of covalent bonding breakage and reorganization, these exchange processes overcome thermodynamic disadvantages, allowing mesoscopic helical chirality to be perfectly preserved. This research highlights the potential of mesoscopic helicity in conferring COFs with favourable chiral properties, providing novel insights into the development of multifunctional COFs in the field of chiral materials chemistry.

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Self‐Assembly of Helical Nanofibrous Chiral Covalent Organic Frameworks

Cited by 32 publications

References 45 publications

Construction of Covalent Organic Frameworks via Multicomponent Reactions

Construction of Covalent Organic Frameworks via Multicomponent Reactions

Sculpting Mesoscopic Helical Chirality into Covalent Organic Framework Nanotubes from Entirely Achiral Building Blocks

Sculpting Mesoscopic Helical Chirality into Covalent Organic Framework Nanotubes from Entirely Achiral Building Blocks

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