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


  • 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).


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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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