Inside/Outside : Post-Synthetic Modification of the Zr-Benzophenonedicarboxylate Metal–Organic Framework

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dc.identifier.uri Mohmeyer, Alexander Schäfer, Malte Schaate, Andreas Locmelis, Sonja Schneider, Andreas M. Behrens, Peter 2021-03-26T08:44:48Z 2021-03-26T08:44:48Z 2020
dc.identifier.citation Mohmeyer, A.: Inside/Outside : Post-Synthetic Modification of the Zr-Benzophenonedicarboxylate Metal–Organic Framework. In: Chemistry - A European Journal 26 (2020), Nr. 10, S. 2222-2232. DOI:
dc.description.abstract The Zr-based metal–organic framework, Zr-bzpdc-MOF, contains the photoreactive linker molecule benzophenone-4,4'-dicarboxylate (bzpdc) which imparts the possibility for photochemical post-synthetic modification. Upon irradiation with UV light, the keto group of the benzophenone moiety will react with nearly every C-H bond-containing molecule. Within this paper, we further explore the photochemical reactivity of the Zr-bzpdc-MOF, especially with regard to which restrictions govern internal versus external reactions. We show that apart from reactions with C-H bond-containing molecules, the MOF reacts also with water. By studying the reactivity versus linear alcohols we find a clear delineation in that shorter alcohol molecules (up to butanol as a borderline case) react with photoexcited keto groups throughout the whole crystals whereas longer ones react only with surface-standing keto groups. In addition, we show that with the alkanes n-butane to n-octane, the reaction is restricted to the outer surface. We hypothesize that the reactivity of the Zr-bzpdc-MOF versus different reagents depends on the accessibility of the pore system which in turn depends mainly on the size of the reagents and on their polarity. The possibility to direct the post-synthetic modification of the Zr-bzpdc-MOF (selective modification of the whole pore system versus surface modification) gives additional degrees of freedom in the design of this metal–organic framework for shaping and for applications. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. eng
dc.language.iso eng
dc.publisher Weinheim : Wiley-VCH Verl.
dc.relation.ispartofseries Chemistry - A European Journal 26 (2020), Nr. 10
dc.rights CC BY 4.0 Unported
dc.subject benzophenone eng
dc.subject modulation eng
dc.subject photochemistry eng
dc.subject post-synthetic modification eng
dc.subject zirconium eng
dc.subject.ddc 540 | Chemie ger
dc.title Inside/Outside : Post-Synthetic Modification of the Zr-Benzophenonedicarboxylate Metal–Organic Framework
dc.type article
dc.type Text
dc.relation.essn 1521-3765
dc.relation.issn 0947-6539
dc.bibliographicCitation.issue 10
dc.bibliographicCitation.volume 26
dc.bibliographicCitation.firstPage 2222
dc.bibliographicCitation.lastPage 2232
dc.description.version publishedVersion
tib.accessRights frei zug�nglich

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