Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant

Timur Islamoglu, Manuel A. Ortuño, Emmanuel Proussaloglou, Ashlee J. Howarth, Nicolaas A. Vermeulen, Ahmet Atilgan, Abdullah M. Asiri, Christopher J. Cramer, Omar K. Farha*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

62 Scopus citations


Amino-functionalized zirconium-based metal-organic frameworks (MOFs) have shown unprecedented catalytic activity compared to non-functionalized analogues for hydrolysis of organophosphonate-based toxic chemicals. Importantly, the effect of the amino group on the catalytic activity is significantly higher in the case of UiO-66-NH2, where the amino groups reside near the node, compared to UiO-67-m-NH2, where they are directed away from the node. Herein, we show that the proximity of the amino group is crucial for fast catalytic activity towards hydrolysis of organophosphonate-based nerve agents. The generality of the observed amine-proximity-dictated catalytic activity has been tested on two different MOF systems which have different topology. DFT calculations reveal that amino groups on all the MOFs studied are not acting as Brønsted bases; instead they control the microsolvation environment at the Zr6-node active site and therefore increase the overall catalytic rates.

Original languageEnglish (US)
Pages (from-to)1949-1953
Number of pages5
JournalAngewandte Chemie - International Edition
Issue number7
StatePublished - Feb 12 2018


  • amino groups
  • heterogeneous catalysis
  • hydrolysis
  • metal–organic frameworks
  • nerve agents

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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