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Article: Organic Counteranion Co-assembly Strategy for the Formation of γ-Cyclodextrin-Containing Hybrid Frameworks

TitleOrganic Counteranion Co-assembly Strategy for the Formation of γ-Cyclodextrin-Containing Hybrid Frameworks
Authors
Issue Date2020
Citation
Journal of the American Chemical Society, 2020, v. 142, n. 4, p. 2042-2050 How to Cite?
AbstractA class of γ-cyclodextrin-containing hybrid frameworks (CD-HFs) has been synthesized, employing γ-cyclodextrin (γ-CD) as the primary building blocks, along with 4-methoxysalicylate (4-MS-) anions as the secondary building blocks. CD-HFs are constructed through the synergistic exploitation of coordinative, electrostatic, and dispersive forces. The syntheses have been carried out using an organic counteranion co-assembly strategy, which allows for the introduction of 4-MS-, in place of inorganic OH-, into the cationic γ-CD-containing metal-organic frameworks (CD-MOFs). Although the packing arrangement of the γ-CD tori in the solid-state superstructure of CD-HFs is identical to that of the previously reported CD-MOFs, CD-HFs crystallize with lower symmetry and in the cuboid space group P43212 - when compared to CD-MOF-1, which has the cubic unit cell of I432 space group - on account of the chiral packing of the 4-MS- anions in the CD-HF superstructures. Importantly, CD-HFs have ultramicroporous apertures associated with the pore channels, a significant deviation from CD-MOF-1, as a consequence of the contribution from the 4-MS- anions, which serve as supramolecular baffles. In gas adsorption-desorption experiments, CD-HF-1 exhibits a Brunauer-Emmett-Teller (BET) surface area of 306 m2 g-1 for CO2 at 195 K, yet does not uptake N2 at 77 K, confirming the difference in porosity between CD-HF-1 and CD-MOF-1. Furthermore, the 4-MS- anions in CD-HF-1 can be exchanged with OH- anions, leading to an irreversible single-crystal to single-crystal transformation, with rearrangement of coordinated metal ions. Reversible transformations were also observed in CD-MOF-1 when OH- ions were exchanged for 4-MS- anions, with the space group changing from I432 to R32. This organic counteranion co-assembly strategy opens up new routes for the construction of hybrid frameworks, which are inaccessible by existing de novo MOF assembly methodologies.
Persistent Identifierhttp://hdl.handle.net/10722/333410
ISSN
2023 Impact Factor: 14.4
2023 SCImago Journal Rankings: 5.489
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorShen, Dengke-
dc.contributor.authorCooper, James A.-
dc.contributor.authorLi, Peng-
dc.contributor.authorGuo, Qing Hui-
dc.contributor.authorCai, Kang-
dc.contributor.authorWang, Xingjie-
dc.contributor.authorWu, Huang-
dc.contributor.authorChen, Hongliang-
dc.contributor.authorZhang, Long-
dc.contributor.authorJiao, Yang-
dc.contributor.authorQiu, Yunyan-
dc.contributor.authorStern, Charlotte L.-
dc.contributor.authorLiu, Zhichang-
dc.contributor.authorSue, Andrew C.H.-
dc.contributor.authorYang, Ying Wei-
dc.contributor.authorAlsubaie, Fehaid M.-
dc.contributor.authorFarha, Omar K.-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-10-06T05:19:10Z-
dc.date.available2023-10-06T05:19:10Z-
dc.date.issued2020-
dc.identifier.citationJournal of the American Chemical Society, 2020, v. 142, n. 4, p. 2042-2050-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10722/333410-
dc.description.abstractA class of γ-cyclodextrin-containing hybrid frameworks (CD-HFs) has been synthesized, employing γ-cyclodextrin (γ-CD) as the primary building blocks, along with 4-methoxysalicylate (4-MS-) anions as the secondary building blocks. CD-HFs are constructed through the synergistic exploitation of coordinative, electrostatic, and dispersive forces. The syntheses have been carried out using an organic counteranion co-assembly strategy, which allows for the introduction of 4-MS-, in place of inorganic OH-, into the cationic γ-CD-containing metal-organic frameworks (CD-MOFs). Although the packing arrangement of the γ-CD tori in the solid-state superstructure of CD-HFs is identical to that of the previously reported CD-MOFs, CD-HFs crystallize with lower symmetry and in the cuboid space group P43212 - when compared to CD-MOF-1, which has the cubic unit cell of I432 space group - on account of the chiral packing of the 4-MS- anions in the CD-HF superstructures. Importantly, CD-HFs have ultramicroporous apertures associated with the pore channels, a significant deviation from CD-MOF-1, as a consequence of the contribution from the 4-MS- anions, which serve as supramolecular baffles. In gas adsorption-desorption experiments, CD-HF-1 exhibits a Brunauer-Emmett-Teller (BET) surface area of 306 m2 g-1 for CO2 at 195 K, yet does not uptake N2 at 77 K, confirming the difference in porosity between CD-HF-1 and CD-MOF-1. Furthermore, the 4-MS- anions in CD-HF-1 can be exchanged with OH- anions, leading to an irreversible single-crystal to single-crystal transformation, with rearrangement of coordinated metal ions. Reversible transformations were also observed in CD-MOF-1 when OH- ions were exchanged for 4-MS- anions, with the space group changing from I432 to R32. This organic counteranion co-assembly strategy opens up new routes for the construction of hybrid frameworks, which are inaccessible by existing de novo MOF assembly methodologies.-
dc.languageeng-
dc.relation.ispartofJournal of the American Chemical Society-
dc.titleOrganic Counteranion Co-assembly Strategy for the Formation of γ-Cyclodextrin-Containing Hybrid Frameworks-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/jacs.9b12527-
dc.identifier.pmid31935077-
dc.identifier.scopuseid_2-s2.0-85078519396-
dc.identifier.volume142-
dc.identifier.issue4-
dc.identifier.spage2042-
dc.identifier.epage2050-
dc.identifier.eissn1520-5126-
dc.identifier.isiWOS:000510531900052-

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