title: A Simple and Non-Destructive Method for Assessing the Incorporation of Bipyridine Dicarboxylates as Linkers within Metal-Organic Frameworks.
abstract: As a novel avenue for applications, metal-organic frameworks (MOFs) are increasingly used for heterogenizing catalytic molecular species as linkers into their crystalline framework. These multifunctional compounds can be accessed with mixed linkers synthesis or postsynthetic-exchange strategies. Major limitations still reside in their challenging characterization; in particular, to provide evidence of the genuine incorporation of the functionalized linkers into the framework and their quantification. Herein, we demonstrate that a combination of computational chemistry, spectroscopy and X-ray diffraction allows access to a non-destructive analysis of mixed-linker UiO-67-type materials featuring biphenyl- and bipyridine-dicarboxylates. Our UV/Vis-based methodology has been further applied to characterize a series of Rh-functionalized UiO-67-type catalysts. The proposed approach allows a recurrent key issue in the characterization of similar supported organometallic systems to be solved.
authors.affiliation: Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK.|Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA, USA.
authors.forename: Christopher H
authors.initials: CH
authors.lastname: Hendon
authors.affiliation: IRCELYON, Institut de Recherche sur la Catalyse et l'Environnement de Lyon, Univ. Lyon 1 - UMR CNRS 5256, 2 av. A. Einstein, 69626, Villeurbanne, France.
authors.forename: Jonathan
authors.initials: J
authors.lastname: Bonnefoy
authors.affiliation: C2P2, Univ. Lyon 1 - UMR CNRS 5265, CPE Lyon, 43 Bd du 11 Novembre 1918, 69616, Villeurbanne, France.
authors.forename: Elsje Alessandra
authors.initials: EA
authors.lastname: Quadrelli
authors.affiliation: IRCELYON, Institut de Recherche sur la Catalyse et l'Environnement de Lyon, Univ. Lyon 1 - UMR CNRS 5256, 2 av. A. Einstein, 69626, Villeurbanne, France.
authors.forename: Jerome
authors.initials: J
authors.lastname: Canivet
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, UPMC Univ Paris 06, Collège de France, 11 Place Marcelin Berthelot, 75231, Paris, France.
authors.forename: Matthew B
authors.initials: MB
authors.lastname: Chambers
authors.affiliation: FRE 3677 "Chimie du Solide et Energie", Collège de France, 11 Place Marcelin Berthelot, 75231, Paris Cedex 05, France.|UPMC Univ Paris 06, Sorbonne Universités, 4 Place Jussieu, 75005, Paris, France.
authors.forename: Gwenaelle
authors.initials: G
authors.lastname: Rousse
authors.affiliation: Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK.
authors.forename: Aron
authors.initials: A
authors.lastname: Walsh
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, UPMC Univ Paris 06, Collège de France, 11 Place Marcelin Berthelot, 75231, Paris, France.
authors.forename: Marc
authors.initials: M
authors.lastname: Fontecave
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, UPMC Univ Paris 06, Collège de France, 11 Place Marcelin Berthelot, 75231, Paris, France.
authors.forename: Caroline
authors.identifier: http://orcid.org/0000-0003-3670-4600
authors.initials: C
authors.lastname: Mellot-Draznieks
keywords: UV/Vis spectroscopy; UiO-67; metal-organic frameworks; mixed linkers; postsynthetic exchange