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Supramolecular Agent–Simulant Correlations for the Luminescence Based Detection of V‐Series Chemical Warfare Agents with Trivalent Lanthanide Complexes
Author(s) -
Dennison Genevieve H.,
Bochet Christian G.,
Curty Christophe,
Ducry Julien,
Nielsen David J.,
Sambrook Mark R.,
Zaugg Andreas,
Johnston Martin R.
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600105
Subject(s) - chemistry , denticity , lanthanide , supramolecular chemistry , amine gas treating , titration , luminescence , chelation , quenching (fluorescence) , chemical warfare agents , inorganic chemistry , fluorescence , photochemistry , polymer chemistry , molecule , organic chemistry , metal , ion , physics , optoelectronics , quantum mechanics , biochemical engineering , engineering
Solution spectroscopic investigations into the interactions of eight potential bidentate V‐series organophosphorus chemical warfare agent (OP CWA) simulants with [Eu(phen) 2 (NO 3 ) 3 ] · 2H 2 O demonstrated that the chemical and structural composition of the secondary binding site within the simulant was of paramount importance. Only simulants containing both phosphoryl/phosphonyl and amine moieties generated analogous spectroscopic behaviours to V‐series OP CWAs seen in previous studies. The results demonstrated that the bidentate chelation mechanism was driven by the phosphoryl/phosphonyl moieties and that the presence of the amine moieties induced a significant secondary dynamic luminescence quenching mechanism. The binding modes of the simulants VO and TEEP to trivalent lanthanides (Eu and La) were further investigated using 1 H and 31 P NMR spectroscopic titrations and kinetic IR experiments. VO, with both the phosphonyl and amine binding sites was found to be the most appropriate simulant for V‐series OP CWAs in supramolecular studies with trivalent lanthanide ions and we recommend VO for use in supramolecular studies of this type.