A Simple and Non-Destructive Method for Assessing the Incorporation of Bipyridine Dicarboxylates as Linkers within Metal-Organic Frameworks

Christopher H. Hendon, Jonathan Bonnefoy, Elsje Alessandra Quadrelli, Jerome Canivet, Matthew B. Chambers, Gwenaelle Rousse, Aron Walsh, Marc Fontecave, Caroline Mellot-Draznieks

Research output: Contribution to journalArticlepeer-review

27 Scopus citations

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.

Original languageEnglish
Pages (from-to)3713-3718
Number of pages6
JournalChemistry - A European Journal
Volume22
Issue number11
DOIs
StatePublished - 7 Mar 2016

Bibliographical note

Funding Information:
The computational work was facilitated by access to the UK National Supercomputer, ARCHER (EPSRC Grant EP/L000202) and XSEDE (NSF Grant ACI-1053575). C.M.D. thank the French National Research Agency (ANR project: HOPFAME ANR-13-BS07-0002-01) and acknowledges support from the Fondation de l''Orangerie (Collège de France) for individual Philanthropy and its donors. Additional support has been received from the Royal Society and the ERC (Grant no. 277757). The IRCELYON thanks its scientific services.

Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords

  • UV/Vis spectroscopy
  • UiO-67
  • metal-organic frameworks
  • mixed linkers
  • postsynthetic exchange

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