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Article: Tröger's Base Chemistry in Solution and in Zr(IV)-Based Metal-Organic Frameworks

TitleTröger's Base Chemistry in Solution and in Zr(IV)-Based Metal-Organic Frameworks
Authors
Issue Date2022
Citation
Journal of the American Chemical Society, 2022, v. 144, n. 49, p. 22574-22581 How to Cite?
AbstractTröger's base (TB) and its derivatives have been studied extensively due to their unique concave shape stemming from the endomethylene strap. However, the strap-clipped TB chemistry has been largely overlooked in metal-organic framework (MOF) solids, leading to a gap in our knowledge within this field. In this work, we report the in situ strap elimination of a carboxylate-carrying TB in the presence of formic acid, both in solution and in Zr(IV)-based MOFs. In the solution system, the methanodiazocine nucleus can be exclusively transformed into an N,N′-diformyl-decorated phenhomazine derivative, regardless of the solvent used (DMF, DMA, or DEF), as unambiguously uncovered by single crystal X-ray crystallography. In contrast, while in the MOF synthetic system, the degree of derivatization reaction can be effectively controlled to give either the secondary diamine or formyl-decorated diamine, depending on the solvent used (DMF or DEF), resulting in the formation of two Zr-MOFs with 8-connected bcu (NU-1900) and 12-connected fcu (NU-407) topologies, respectively. The derivatization mechanism is proposed to be topology-guided and dependent on the local acid concentration during the MOF formation processes. Moreover, we discovered a novel post-synthetically water-induced in situ linker formylation process in NU-1900 through sequential formic acid elimination, migration, and condensation processes, affording an isostructural framework with the same linker as in NU-407, which further corroborates our proposed mechanism. Additionally, the highly defective NU-1900 with abundant accessible Zr sites was demonstrated to be an outstanding catalyst for the detoxification of a nerve agent simulant with a half-life of less than 1 min.
Persistent Identifierhttp://hdl.handle.net/10722/333570
ISSN
2023 Impact Factor: 14.4
2023 SCImago Journal Rankings: 5.489

 

DC FieldValueLanguage
dc.contributor.authorGong, Wei-
dc.contributor.authorKazem-Rostami, Masoud-
dc.contributor.authorSon, Florencia A.-
dc.contributor.authorSu, Shengyi-
dc.contributor.authorFahy, Kira M.-
dc.contributor.authorXie, Haomiao-
dc.contributor.authorIslamoglu, Timur-
dc.contributor.authorLiu, Yan-
dc.contributor.authorStoddart, J. Fraser-
dc.contributor.authorCui, Yong-
dc.contributor.authorFarha, Omar K.-
dc.date.accessioned2023-10-06T05:20:40Z-
dc.date.available2023-10-06T05:20:40Z-
dc.date.issued2022-
dc.identifier.citationJournal of the American Chemical Society, 2022, v. 144, n. 49, p. 22574-22581-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10722/333570-
dc.description.abstractTröger's base (TB) and its derivatives have been studied extensively due to their unique concave shape stemming from the endomethylene strap. However, the strap-clipped TB chemistry has been largely overlooked in metal-organic framework (MOF) solids, leading to a gap in our knowledge within this field. In this work, we report the in situ strap elimination of a carboxylate-carrying TB in the presence of formic acid, both in solution and in Zr(IV)-based MOFs. In the solution system, the methanodiazocine nucleus can be exclusively transformed into an N,N′-diformyl-decorated phenhomazine derivative, regardless of the solvent used (DMF, DMA, or DEF), as unambiguously uncovered by single crystal X-ray crystallography. In contrast, while in the MOF synthetic system, the degree of derivatization reaction can be effectively controlled to give either the secondary diamine or formyl-decorated diamine, depending on the solvent used (DMF or DEF), resulting in the formation of two Zr-MOFs with 8-connected bcu (NU-1900) and 12-connected fcu (NU-407) topologies, respectively. The derivatization mechanism is proposed to be topology-guided and dependent on the local acid concentration during the MOF formation processes. Moreover, we discovered a novel post-synthetically water-induced in situ linker formylation process in NU-1900 through sequential formic acid elimination, migration, and condensation processes, affording an isostructural framework with the same linker as in NU-407, which further corroborates our proposed mechanism. Additionally, the highly defective NU-1900 with abundant accessible Zr sites was demonstrated to be an outstanding catalyst for the detoxification of a nerve agent simulant with a half-life of less than 1 min.-
dc.languageeng-
dc.relation.ispartofJournal of the American Chemical Society-
dc.titleTröger's Base Chemistry in Solution and in Zr(IV)-Based Metal-Organic Frameworks-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/jacs.2c08623-
dc.identifier.pmid36454651-
dc.identifier.scopuseid_2-s2.0-85143413549-
dc.identifier.volume144-
dc.identifier.issue49-
dc.identifier.spage22574-
dc.identifier.epage22581-
dc.identifier.eissn1520-5126-

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