Tuning Adsorption-Induced Responsiveness of a Flexible Metal–Organic Framework JUK-8 by Linker Halogenation - Archive ouverte HAL
Article Dans Une Revue Chemistry of Materials Année : 2022

Tuning Adsorption-Induced Responsiveness of a Flexible Metal–Organic Framework JUK-8 by Linker Halogenation

Résumé

Flexible stimuli-responsive metal−organic frameworks have become promising candidates for numerous applications in gas-related technologies; however, the methods of fine tuning their responses are still limited and sought after. In this work, we demonstrate control over the adsorption properties of a flexible platform by incorporating halogen substituents (X = F, Cl, Br, I) into an eightfold interpenetrated isoreticular series [Zn(oba)(X-pip)] n (JUK-8X; X-pip = 4-pyridyl-functionalized benzene-1,3-dicarbo-5-halogenohydrazide; oba 2− = 4,4′-oxydibenzoic carboxylate). The introduced halogen atoms allow for precise tuning of CO 2 gate-opening pressures from p/p 0 = 0.08 for the parental JUK-8 to 0.78 for the chlorinefunctionalized JUK-8Cl. The presence of fluorine or chlorine substituent in the X-pip linker practically does not influence the maximum molar CO 2 uptake as compared to JUK-8, whereas larger bromine or iodine atoms increase this uptake by 59 and 48%, respectively. Utilizing in situ powder X-ray diffraction (PXRD) during CO 2 adsorption for a model JUK-8F, we propose a detailed mechanism of phase transitions including positions of the adsorbed gas molecules for the two loaded phases. Density functional theory calculations supported by in situ PXRD measurements at a saturation pressure shed light on the unusual CO 2 adsorption properties of JUK-8Br and JUK-8I. Overall, our report demonstrates the use of halogen interactions for the control of a gas-responsive system and provides insightful guidance for the further development of flexible, adaptable materials.

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hal-04044897 , version 1 (24-03-2023)

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Kornel Roztocki, Filip Formalik, Volodymyr Bon, Anna Krawczuk, Piotr Goszczycki, et al.. Tuning Adsorption-Induced Responsiveness of a Flexible Metal–Organic Framework JUK-8 by Linker Halogenation. Chemistry of Materials, 2022, 34 (7), pp.3430-3439. ⟨10.1021/acs.chemmater.2c00249⟩. ⟨hal-04044897⟩
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