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

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

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-NH 2 , where the amino groups reside near the node, compared to UiO-67-m-NH 2 , 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 Zr 6 -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
Volume57
Issue number7
DOIs
StatePublished - Feb 12 2018

Fingerprint

Amines
Hydrolysis
Catalyst activity
Organophosphonates
Metals
Poisons
Zirconium
Discrete Fourier transforms
Topology
Nerve Agents

Keywords

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

PubMed: MeSH publication types

  • Journal Article
  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

Cite this

Islamoglu, T., Ortuño, M. A., Proussaloglou, E., Howarth, A. J., Vermeulen, N. A., Atilgan, A., ... Farha, O. K. (2018). Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant. Angewandte Chemie - International Edition, 57(7), 1949-1953. https://doi.org/10.1002/anie.201712645

Presence versus Proximity : The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant. / Islamoglu, Timur; Ortuño, Manuel A.; Proussaloglou, Emmanuel; Howarth, Ashlee J.; Vermeulen, Nicolaas A.; Atilgan, Ahmet; Asiri, Abdullah M.; Cramer, Christopher J.; Farha, Omar K.

In: Angewandte Chemie - International Edition, Vol. 57, No. 7, 12.02.2018, p. 1949-1953.

Research output: Contribution to journalArticle

Islamoglu, T, Ortuño, MA, Proussaloglou, E, Howarth, AJ, Vermeulen, NA, Atilgan, A, Asiri, AM, Cramer, CJ & Farha, OK 2018, 'Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant', Angewandte Chemie - International Edition, vol. 57, no. 7, pp. 1949-1953. https://doi.org/10.1002/anie.201712645
Islamoglu, Timur ; Ortuño, Manuel A. ; Proussaloglou, Emmanuel ; Howarth, Ashlee J. ; Vermeulen, Nicolaas A. ; Atilgan, Ahmet ; Asiri, Abdullah M. ; Cramer, Christopher J. ; Farha, Omar K. / Presence versus Proximity : The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant. In: Angewandte Chemie - International Edition. 2018 ; Vol. 57, No. 7. pp. 1949-1953.
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