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

Northwestern University
Fudan University
Westlake University
Tianjin University
Jilin University
King Abdulaziz City for Science and Technology
University of New South Wales

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

42 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
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 - 29 Jan 2020
Externally published	Yes

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10.1021/jacs.9b12527

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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{d59ccd5df8f64575b6a88af8866e8632,

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,

day = "29",

doi = "10.1021/jacs.9b12527",

language = "英语",

volume = "142",

pages = "2042--2050",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "4",

}

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.

UR - https://www.scopus.com/pages/publications/85078519396

U2 - 10.1021/jacs.9b12527

DO - 10.1021/jacs.9b12527

M3 - 文章

C2 - 31935077

AN - SCOPUS:85078519396

SN - 0002-7863

VL - 142

SP - 2042

EP - 2050

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 4

ER -

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

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