Hydrogen-bonding interactions in crown-(thio)urea complexes with anions, chemical warfare agents and simulants

Hannah Cave, Jayne A. Ede, Mark Sambrook, Howard Dodd, Flavia Fucassi, Alexander Cragg, Adam Lansley, Peter Cragg

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Benzocrown ethers incorporating phenyl and nitrophenyl urea and thiourea moieties were synthesised. Both the nitrophenyl urea and thiourea derivative gave a fluoride-specific colorimetric response but only the urea derivative bound the organophosphonate nerve agent simulants dimethyl methylphosphonate (DMMP) and diisopropyl methylphosphonate (DIMP). This suggested an application as sensors for the nerve agents sarin, soman and cyclosarin which release fluoride upon hydrolysis. Although no fluoride-induced response was observed in the UV-visible spectrum, binding to soman was determined by 1H NMR. DFT computational simulations suggested that the two crowns adopt different conformations in which both can bind fluoride but only the urea derivative can bind DMMP, DIMP and soman. The results show that, for this system, simulant- and soman-binding behaviours are in good agreement.
Original languageEnglish
Pages (from-to)703-712
Number of pages10
JournalSupramolecular Chemistry
Volume31
Issue number11
DOIs
Publication statusPublished - 1 Sep 2019

Fingerprint

Chemical Warfare Agents
Soman
Fluorides
Anions
Urea
Hydrogen bonds
Thiourea
Derivatives
Sarin
Organophosphonates
Ethers
Discrete Fourier transforms
Conformations
Hydrolysis
Nuclear magnetic resonance
Sensors

Keywords

  • Chemical warfare agents
  • colorimetric sensors
  • hydrogen bonding
  • macrocycles
  • simulants

Cite this

Cave, Hannah ; Ede, Jayne A. ; Sambrook, Mark ; Dodd, Howard ; Fucassi, Flavia ; Cragg, Alexander ; Lansley, Adam ; Cragg, Peter. / Hydrogen-bonding interactions in crown-(thio)urea complexes with anions, chemical warfare agents and simulants. In: Supramolecular Chemistry. 2019 ; Vol. 31, No. 11. pp. 703-712.
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Hydrogen-bonding interactions in crown-(thio)urea complexes with anions, chemical warfare agents and simulants. / Cave, Hannah; Ede, Jayne A.; Sambrook, Mark; Dodd, Howard; Fucassi, Flavia; Cragg, Alexander; Lansley, Adam; Cragg, Peter.

In: Supramolecular Chemistry, Vol. 31, No. 11, 01.09.2019, p. 703-712.

Research output: Contribution to journalArticleResearchpeer-review

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AU - Ede, Jayne A.

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AU - Cragg, Peter

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