Inside/outside

Post-synthetic modification of the Zr-benzophenonedicarboxylate metal–organic framework

verfasst von

Alexander Mohmeyer, Malte Schäfer, Andreas Schaate, Sonja Locmelis, Andreas M. Schneider, Peter Behrens

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.

Organisationseinheit(en)

Institut für Anorganische Chemie
PhoenixD: Simulation, Fabrikation und Anwendung optischer Systeme

Typ

Artikel

Journal

Chemistry - a European journal

Band

26

Seiten

2222-2232

Anzahl der Seiten

11

ISSN

0947-6539

Publikationsdatum

04.02.2020

Publikationsstatus

Veröffentlicht

Peer-reviewed

Ja

ASJC Scopus Sachgebiete

Katalyse, Organische Chemie

Elektronische Version(en)

https://doi.org/10.1002/chem.201903630 (Zugang: Offen)