Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks

Claire L. Hobday, Thomas D. Bennett, David Fairen-Jimenez, Alexander J. Graham, Carole A. Morrison, David R. Allan, Tina Duren, Stephen A. Moggach

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Many zeolitic imidazolate frameworks (ZIFs) are promising candidates for use in separation technologies. Comprising large cavities interconnected by small windows they can be used, at least in principle, as molecular sieves where molecules smaller than the window size are able to diffuse into the material while larger molecules are rejected. However, "swing effect" or "gate opening" phenomena resulting in an enlargement of the windows have proven to be detrimental. Here, we present the first systematic experimental and computational study of the effect of chemical functionalization of the imidazole linker on the framework dynamics. Using high-pressure (HP) single-crystal X-ray diffraction, density functional theory, and grand canonical Monte Carlo simulations, we show that in the isostructural ZIF-8, ZIF-90, and ZIF-65 functional groups of increasing polarity (-CH3, -CHO, and -NO2) on the imidazole linkers provide control over the degree of rotation and thus the critical window diameter. On application of pressure, the substituted imidazolate rings rotate, resulting in an increase in both pore volume and content. Our results show that the interplay between the guest molecules and the chemical function of the imidazole linker is essential for directing the swing effect in ZIF frameworks and therefore the adsorption performance.

Original languageEnglish
Pages (from-to)382-387
Number of pages6
JournalJournal of the American Chemical Society
Volume140
Issue number1
DOIs
Publication statusPublished - 10 Jan 2018
Externally publishedYes

Cite this

Hobday, C. L., Bennett, T. D., Fairen-Jimenez, D., Graham, A. J., Morrison, C. A., Allan, D. R., ... Moggach, S. A. (2018). Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks. Journal of the American Chemical Society, 140(1), 382-387. https://doi.org/10.1021/jacs.7b10897
Hobday, Claire L. ; Bennett, Thomas D. ; Fairen-Jimenez, David ; Graham, Alexander J. ; Morrison, Carole A. ; Allan, David R. ; Duren, Tina ; Moggach, Stephen A. / Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 1. pp. 382-387.
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Hobday, CL, Bennett, TD, Fairen-Jimenez, D, Graham, AJ, Morrison, CA, Allan, DR, Duren, T & Moggach, SA 2018, 'Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks' Journal of the American Chemical Society, vol. 140, no. 1, pp. 382-387. https://doi.org/10.1021/jacs.7b10897

Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks. / Hobday, Claire L.; Bennett, Thomas D.; Fairen-Jimenez, David; Graham, Alexander J.; Morrison, Carole A.; Allan, David R.; Duren, Tina; Moggach, Stephen A.

In: Journal of the American Chemical Society, Vol. 140, No. 1, 10.01.2018, p. 382-387.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks

AU - Hobday, Claire L.

AU - Bennett, Thomas D.

AU - Fairen-Jimenez, David

AU - Graham, Alexander J.

AU - Morrison, Carole A.

AU - Allan, David R.

AU - Duren, Tina

AU - Moggach, Stephen A.

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N2 - Many zeolitic imidazolate frameworks (ZIFs) are promising candidates for use in separation technologies. Comprising large cavities interconnected by small windows they can be used, at least in principle, as molecular sieves where molecules smaller than the window size are able to diffuse into the material while larger molecules are rejected. However, "swing effect" or "gate opening" phenomena resulting in an enlargement of the windows have proven to be detrimental. Here, we present the first systematic experimental and computational study of the effect of chemical functionalization of the imidazole linker on the framework dynamics. Using high-pressure (HP) single-crystal X-ray diffraction, density functional theory, and grand canonical Monte Carlo simulations, we show that in the isostructural ZIF-8, ZIF-90, and ZIF-65 functional groups of increasing polarity (-CH3, -CHO, and -NO2) on the imidazole linkers provide control over the degree of rotation and thus the critical window diameter. On application of pressure, the substituted imidazolate rings rotate, resulting in an increase in both pore volume and content. Our results show that the interplay between the guest molecules and the chemical function of the imidazole linker is essential for directing the swing effect in ZIF frameworks and therefore the adsorption performance.

AB - Many zeolitic imidazolate frameworks (ZIFs) are promising candidates for use in separation technologies. Comprising large cavities interconnected by small windows they can be used, at least in principle, as molecular sieves where molecules smaller than the window size are able to diffuse into the material while larger molecules are rejected. However, "swing effect" or "gate opening" phenomena resulting in an enlargement of the windows have proven to be detrimental. Here, we present the first systematic experimental and computational study of the effect of chemical functionalization of the imidazole linker on the framework dynamics. Using high-pressure (HP) single-crystal X-ray diffraction, density functional theory, and grand canonical Monte Carlo simulations, we show that in the isostructural ZIF-8, ZIF-90, and ZIF-65 functional groups of increasing polarity (-CH3, -CHO, and -NO2) on the imidazole linkers provide control over the degree of rotation and thus the critical window diameter. On application of pressure, the substituted imidazolate rings rotate, resulting in an increase in both pore volume and content. Our results show that the interplay between the guest molecules and the chemical function of the imidazole linker is essential for directing the swing effect in ZIF frameworks and therefore the adsorption performance.

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KW - SEPARATION

KW - AMORPHIZATION

KW - CRYSTALS

KW - FLUIDS

KW - PHASE

U2 - 10.1021/jacs.7b10897

DO - 10.1021/jacs.7b10897

M3 - Article

VL - 140

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EP - 387

JO - Journal of the Amercian Chemical Society

JF - Journal of the Amercian Chemical Society

SN - 0002-7863

IS - 1

ER -

Hobday CL, Bennett TD, Fairen-Jimenez D, Graham AJ, Morrison CA, Allan DR et al. Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks. Journal of the American Chemical Society. 2018 Jan 10;140(1):382-387. https://doi.org/10.1021/jacs.7b10897