Chromogenic Detection of the Organophosphorus Nerve Agent Simulant DCP Mediated by Rhodium(II,II) Paddlewheel Complexes

• Published in: ACS sensors 2024-05, Vol.9 (5), p.2325-2333
• Main Authors: Fussell, Eric D., Kline, Neal D., Bennin, Ernest, Hirschbeck, Sarah S., Darko, Ampofo
• Format: Article
• Language: English
• Subjects: Chemical Warfare Agents - analysis; Chemical Warfare Agents - chemistry; Chromogenic Compounds - chemistry; Coordination Complexes - chemistry; Limit of Detection; Nerve Agents - analysis; Nerve Agents - chemistry; Organophosphorus Compounds - analysis; Organophosphorus Compounds - chemistry; Rhodium - chemistry
• ISSN: 2379-3694; 2379-3694
• DOI: 10.1021/acssensors.3c01993

Organophosphorus nerve agents (OPNAs) pose a great threat to humanity. Possessing extreme toxicity, rapid lethality, and an unassuming appearance, these chemical warfare agents must be quickly and selectively identified so that treatment can be administered to those affected. Chromogenic detection is the most convenient form of OPNA detection, but current methods suffer from false positives. Here, nitrogenous base adducts of dirhodium­(II,II) acetate were synthesized and used as chromogenic detectors of diethyl chlorophosphate (DCP), an OPNA simulant. UV–vis spectrophotometry was used to evaluate the sensitivity and selectivity of the complexes in the detection of DCP. Visual limits of detection (LOD) for DCP were as low as 1.5 mM DCP, while UV–vis-based LODs were as low as 0.113 μM. The dirhodium­(II,II) complexes were also tested with several potential interferents, none of which produced a visual color change that could be mistaken for OPNA response. Ultimately, the Rh2(OAc)4(1,8-diazabicyclo­[5.4.0]­undec-7-ene)2 complex showed the best combination of detection capability and interferent resistance. These results, when taken together, show that dirhodium­(II,II) paddlewheel complexes with nitrogenous base adducts can produce instant, selective, and sensitive detection of DCP. It is our aim to further explore and apply this new motif to produce even more capable OPNA sensors.