Communication

Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal–Organic Frameworks†

  1. Frederik Vermoortele1,
  2. Matthias Vandichel2,
  3. Ben Van de Voorde1,
  4. Dr. Rob Ameloot1,
  5. Prof. Michel Waroquier2,
  6. Prof. Veronique Van Speybroeck2,*,
  7. Prof. Dirk E. De Vos1,*

Article first published online: 5 APR 2012

DOI: 10.1002/anie.201108565

Issue

Angewandte Chemie International Edition

Angewandte Chemie International Edition

Volume 51, Issue 20, pages 4887–4890, May 14, 2012

Additional Information

How to Cite

Vermoortele, F., Vandichel, M., Van de Voorde, B., Ameloot, R., Waroquier, M., Van Speybroeck, V. and De Vos, D. E. (2012), Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal–Organic Frameworks. Angew. Chem. Int. Ed., 51: 4887–4890. doi: 10.1002/anie.201108565

Author Information

  1. 1

    Centre for Surface Chemistry and Catalysis, Katholieke Universiteit Leuven, Kasteelpark Arenberg 23, 3001 Leuven (Belgium)

  2. 2

    Center for Molecular Modeling, Universiteit Gent, Technologiepark 903, 9052 Zwijnaarde (Belgium)

*Center for Molecular Modeling, Universiteit Gent, Technologiepark 903, 9052 Zwijnaarde (Belgium)

  1. †

    We are grateful to FWO, the Belspo (IAP 6/27), to KULeuven (CASAS Methusalem grant) and the Research Board of Ghent University (BOF) for project support. Funding was also received from the European Research Council under the European Community’s Seventh Framework Programme [FP7(2007-2013) ERC grant agreement number 240483]. R.A. is a post-doctoral fellow of FWO. The computational resources were provided by Ghent University (Stevin Supercomputer Infrastructure).

Publication History

  1. Issue published online: 8 MAY 2012
  2. Article first published online: 5 APR 2012
  3. Manuscript Received: 5 DEC 2011

Funded by

  • FWO
  • Belspo. Grant Number: IAP 6/27
  • KULeuven
  • Research Board of Ghent University
  • European Research Council. Grant Number: 240483

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Keywords:

  • heterogeneous catalysis;
  • Lewis acidity;
  • metal–organic framework;
  • structure–activity relationships;
  • substituent effects
Thumbnail image of graphical abstract

Functionalized linkers can greatly increase the activity of metal–organic framework (MOF) catalysts with coordinatively unsaturated sites. A clear linear free-energy relationship (LFER) was found between Hammett σm values of the linker substituents X and the rate kX of a carbonyl-ene reaction. This is the first LFER ever observed for MOF catalysts. A 56-fold increase in rate was found when the substituent is a nitro group (see picture).

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