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

Abstract

Here, a 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 andmore » CD-MOF-1. Additionally, 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.« less

Authors:

Shen, Dengke ^[1]; Cooper, James A.  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-3981-9246"

Li, Peng  ^[2];

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Guo, Qing-Hui  ^[1];

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Cai, Kang  ^[1];

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Wang, Xingjie  ^[1];

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Wu, Huang ^[1]; Chen, Hongliang ^[1]; Zhang, Long ^[1]; Jiao, Yang ^[1]; Qiu, Yunyan  ^[1];

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Stern, Charlotte L. ^[1]; Liu, Zhichang  ^[3];

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Sue, Andrew C. -H.  ^[4];

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Yang, Ying-Wei  ^[5];

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Alsubaie, Fehaid M. ^[6]; Farha, Omar K.  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-9904-9845"

Stoddart, J. Fraser  ^[7]

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+ Show Author Affiliations

1. Northwestern Univ., Evanston, IL (United States)
2. Fudan Univ., Shanghai (China)
3. Westlake Univ., Hangzhou (China)
4. Tianjin Univ. (China)
5. Jilin Univ., Changchun (China)
6. Joint Center of Excellence in Integrated Nanosystems, King Abdulaziz City for Science and Technology, Riyadh 11442, Kingdom of Saudi Arabia
7. Northwestern Univ., Evanston, IL (United States); Tianjin Univ. (China); Univ. of New South Wales, Sydney, NSW (Australia)

Publication Date:

Tue Jan 14 00:00:00 EST 2020

Research Org.:

Univ. of Notre Dame, IN (United States)

Sponsoring Org.:

USDOE National Nuclear Security Administration (NNSA); National Natural Science Foundation of China (NSFC); National Basic Research Program of China

OSTI Identifier:

1597703

Grant/Contract Number:  

NA0003763

Resource Type:

Accepted Manuscript

Journal Name:

Journal of the American Chemical Society

Additional Journal Information:

Journal Volume: 142; Journal Issue: 4; Journal ID: ISSN 0002-7863

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; Crystals; Superstructures; Anions; Oligomers Ions