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

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 methylphosphona...

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Bibliographic Details
Published in:Supramolecular chemistry 2019-11, Vol.31 (11), p.703-712
Main Authors: Cave, Hannah, Ede, Jayne A., Sambrook, Mark R., Dodd, Howard, Fucassi, Flavia, Cragg, Alexander S., Lansley, Adam H., Cragg, Peter J.
Format: Article
Language:English
Subjects:
Binding
Biological & chemical weapons
Bonding agents
Chemical warfare
Chemical warfare agents
colorimetric sensors
Colorimetry
Computer simulation
Ethers
Fluorides
Hydrogen bonding
macrocycles
NMR
Nuclear magnetic resonance
Organic chemistry
Sarin
simulants
Thiourea derivatives
Thioureas
Ureas
Visible spectrum
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Summary: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 1 H 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.
ISSN:1061-0278
1029-0478
DOI:10.1080/10610278.2019.1659268