Abstract
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 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.
Original language | English (US) |
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Pages (from-to) | 2042-2050 |
Number of pages | 9 |
Journal | Journal of the American Chemical Society |
Volume | 142 |
Issue number | 4 |
DOIs | |
State | Published - Jan 29 2020 |
Funding
This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). The authors would like to thank KACST, NU, Tianjin University, and the University of New South Wales for their continued support of this research. This work made use of the IMSERC at Northwestern University, which has received support from the State of Illinois and International Institute for Nanotechnology (IIN). Z.L. acknowledges financial support from the National Natural Science Foundation of China (No. 21971211). Y.-W.Y. acknowledges support from the Jilin University Talents Cultivation Program. O.K.F. and P.L. gratefully acknowledge support from the U.S. Department of Energy, National Nuclear Security Administration, under Award Number DE-NA0003763. This work was also supported by the 973 National Basic Research Program of China (2015CB856500).
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry
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CCDC 1980724: Experimental Crystal Structure Determination
Shen, D. (Contributor), Cooper, J. A. (Contributor), Li, P. (Contributor), Guo, Q.-H. (Contributor), Cai, K. (Contributor), Wang, X. (Contributor), Wu, H. (Contributor), Chen, H. (Contributor), Zhang, L. (Contributor), Jiao, Y. (Contributor), Qiu, Y. (Contributor), Stern, C. L. (Contributor), Liu, Z. (Contributor), Sue, A.C.-H. (Contributor), Yang, Y.-W. (Contributor), Alsubaie, F. M. (Contributor), Farha, O. K. (Contributor) & Stoddart, J. F. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc24h3b3, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc24h3b3&sid=DataCite
Dataset
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CCDC 1980722: Experimental Crystal Structure Determination
Shen, D. (Contributor), Cooper, J. A. (Contributor), Li, P. (Contributor), Guo, Q.-H. (Contributor), Cai, K. (Contributor), Wang, X. (Contributor), Wu, H. (Contributor), Chen, H. (Contributor), Zhang, L. (Contributor), Jiao, Y. (Contributor), Qiu, Y. (Contributor), Stern, C. L. (Contributor), Liu, Z. (Contributor), Sue, A.C.-H. (Contributor), Yang, Y.-W. (Contributor), Alsubaie, F. M. (Contributor), Farha, O. K. (Contributor) & Stoddart, J. F. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc24h381, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc24h381&sid=DataCite
Dataset
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CCDC 1980725: Experimental Crystal Structure Determination
Shen, D. (Contributor), Cooper, J. A. (Contributor), Li, P. (Contributor), Guo, Q.-H. (Contributor), Cai, K. (Contributor), Wang, X. (Contributor), Wu, H. (Contributor), Chen, H. (Contributor), Zhang, L. (Contributor), Jiao, Y. (Contributor), Qiu, Y. (Contributor), Stern, C. L. (Contributor), Liu, Z. (Contributor), Sue, A.C.-H. (Contributor), Yang, Y.-W. (Contributor), Alsubaie, F. M. (Contributor), Farha, O. K. (Contributor) & Stoddart, J. F. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc24h3c4, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc24h3c4&sid=DataCite
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