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‐complementary
This content will become publicly available on November 1, 2024
Dithienylethenes (DTEs) are a promising class of organic photoswitches that can be used to create crystalline solids with properties controlled by light. However, the ability of DTEs to adopt multiple conformations, only one of which is photoactive, complicates the rational design of these materials. Herein, the synthesis and structural characterization of 19 crystalline solids containing a single DTE molecule are described. A novel
- Award ID(s):
- 1834750
- NSF-PAR ID:
- 10491731
- Publisher / Repository:
- International Union of Crystallography (IUCr)
- Date Published:
- Journal Name:
- IUCrJ
- Volume:
- 10
- Issue:
- 6
- ISSN:
- 2052-2525
- Page Range / eLocation ID:
- 694 to 699
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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‐complementary
ortho ‐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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