Tuning Adsorption-Induced Responsiveness of a Flexible Metal–Organic Framework JUK-8 by Linker Halogenation
Publikation: Beitrag in Fachzeitschrift › Forschungsartikel › Beigetragen › Begutachtung
Beitragende
Abstract
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; oba2- = 4,4′-oxydibenzoic carboxylate). The introduced halogen atoms allow for precise tuning of CO2 gate-opening pressures from p/p0 = 0.08 for the parental JUK-8 to 0.78 for the chlorine-functionalized JUK-8Cl. The presence of fluorine or chlorine substituent in the X-pip linker practically does not influence the maximum molar CO2 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 CO2 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 CO2 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.
Details
Originalsprache | Englisch |
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Seiten (von - bis) | 3430-3439 |
Seitenumfang | 10 |
Fachzeitschrift | Chemistry of materials |
Jahrgang | 34 |
Ausgabenummer | 7 |
Publikationsstatus | Veröffentlicht - 12 Apr. 2022 |
Peer-Review-Status | Ja |
Externe IDs
Scopus | 85127870433 |
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WOS | 000813329700001 |
Mendeley | 91321191-9b51-3500-8313-e1a539a489be |
unpaywall | 10.1021/acs.chemmater.2c00249 |