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

Dengke Shen; James A. Cooper; Peng Li; Qing Hui Guo; Kang Cai; Xingjie Wang; Huang Wu; Hongliang Chen; Long Zhang; Yang Jiao; Yunyan Qiu; Charlotte L. Stern; Zhichang Liu; Andrew C.H. Sue; Ying Wei Yang; Fehaid M. Alsubaie; Omar K. Farha; J. Fraser Stoddart

doi:10.1021/jacs.9b12527

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

Dengke Shen, James A. Cooper, Peng Li, Qing Hui Guo, Kang Cai, Xingjie Wang, Huang Wu, Hongliang Chen, Long Zhang, Yang Jiao, Yunyan Qiu, Charlotte L. Stern, Zhichang Liu, Andrew C.H. Sue, Ying Wei Yang, Fehaid M. Alsubaie, Omar K. Farha, J. Fraser Stoddart^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

36 Scopus citations

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)
Pages (from-to)	2042-2050
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	142
Issue number	4
DOIs	https://doi.org/10.1021/jacs.9b12527
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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10.1021/jacs.9b12527

Cite this

Shen, D., Cooper, J. A., Li, P., Guo, Q. H., Cai, K., Wang, X., Wu, H., Chen, H., Zhang, L., Jiao, Y., Qiu, Y., Stern, C. L., Liu, Z., Sue, A. C. H., Yang, Y. W., Alsubaie, F. M., Farha, O. K., & Stoddart, J. F. (2020). Organic Counteranion Co-assembly Strategy for the Formation of γ-Cyclodextrin-Containing Hybrid Frameworks. Journal of the American Chemical Society, 142(4), 2042-2050. https://doi.org/10.1021/jacs.9b12527

@article{f845b0021afd4b06afc64547c30fe2bc,

title = "Organic Counteranion Co-assembly Strategy for the Formation of γ-Cyclodextrin-Containing Hybrid Frameworks",

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.",

author = "Dengke Shen and Cooper, {James A.} and Peng Li and Guo, {Qing Hui} and Kang Cai and Xingjie Wang and Huang Wu and Hongliang Chen and Long Zhang and Yang Jiao and Yunyan Qiu and Stern, {Charlotte L.} and Zhichang Liu and Sue, {Andrew C.H.} and Yang, {Ying Wei} and Alsubaie, {Fehaid M.} and Farha, {Omar K.} and Stoddart, {J. Fraser}",

note = "Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = jan,

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doi = "10.1021/jacs.9b12527",

language = "English (US)",

volume = "142",

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Shen, D, Cooper, JA, Li, P, Guo, QH, Cai, K, Wang, X, Wu, H, Chen, H, Zhang, L, Jiao, Y, Qiu, Y, Stern, CL, Liu, Z, Sue, ACH, Yang, YW, Alsubaie, FM, Farha, OK & Stoddart, JF 2020, 'Organic Counteranion Co-assembly Strategy for the Formation of γ-Cyclodextrin-Containing Hybrid Frameworks', Journal of the American Chemical Society, vol. 142, no. 4, pp. 2042-2050. https://doi.org/10.1021/jacs.9b12527

TY - JOUR

T1 - Organic Counteranion Co-assembly Strategy for the Formation of γ-Cyclodextrin-Containing Hybrid Frameworks

AU - Shen, Dengke

AU - Cooper, James A.

AU - Li, Peng

AU - Guo, Qing Hui

AU - Cai, Kang

AU - Wang, Xingjie

AU - Wu, Huang

AU - Chen, Hongliang

AU - Zhang, Long

AU - Jiao, Yang

AU - Qiu, Yunyan

AU - Stern, Charlotte L.

AU - Liu, Zhichang

AU - Sue, Andrew C.H.

AU - Yang, Ying Wei

AU - Alsubaie, Fehaid M.

AU - Farha, Omar K.

AU - Stoddart, J. Fraser

PY - 2020/1/29

Y1 - 2020/1/29

N2 - 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.

AB - 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.

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

Abstract

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

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ASJC Scopus subject areas

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CCDC 1980724: Experimental Crystal Structure Determination

CCDC 1980722: Experimental Crystal Structure Determination

CCDC 1980725: Experimental Crystal Structure Determination

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