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This content will become publicly available on October 23, 2024

Title: Ortho ‐Alkoxy‐benzamide Directed Formation of a Single Crystalline Hydrogen‐bonded Crosslinked Organic Framework and Its Boron Trifluoride Uptake and Catalysis
Abstract

Boron trifluoride (BF3) is a highly corrosive gas widely used in industry. Confining BF3in porous materials ensures safe and convenient handling and prevents its degradation. Hence, it is highly desired to develop porous materials with high adsorption capacity, high stability, and resistance to BF3corrosion. Herein, we designed and synthesized a Lewis basic single‐crystalline hydrogen‐bond crosslinked organic framework (HCOF‐50) for BF3storage and its application in catalysis. Specifically, we introduced self‐complementaryortho‐alkoxy‐benzamide hydrogen‐bonding moieties to direct the formation of highly organized hydrogen‐bonded networks, which were subsequently photo‐crosslinked to generate HCOFs. The HCOF‐50 features Lewis basic thioether linkages and electron‐rich pore surfaces for BF3uptake. As a result, HCOF‐50 shows a record‐high 14.2 mmol/g BF3uptake capacity. The BF3uptake in HCOF‐50 is reversible, leading to the slow release of BF3. We leveraged this property to reduce the undesirable chain transfer and termination in the cationic polymerization of vinyl ethers. Polymers with higher molecular weights and lower polydispersity were generated compared to those synthesized using BF3 ⋅ Et2O. The elucidation of the structure–property relationship, as provided by the single‐crystal X‐ray structures, combined with the high BF3uptake capacity and controlled sorption, highlights the molecular understanding of framework‐guest interactions in addressing contemporary challenges.

 
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Award ID(s):
2413574
NSF-PAR ID:
10478224
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Angewandte Chemie International Edition
Volume:
62
Issue:
50
ISSN:
1433-7851
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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