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Selective Sensing of a Nerve Agent Simulant via Dirhodium(II,II) Paddlewheel Complexes Featuring Pendant Hemilabile
Desiree Moore1, Eric D Fussell1, Neal D Kline2
1Department of Chemistry, University of Tennessee, 1420 Circle Drive, Knoxville, Tennessee 37996, United States.
Abstract:
Herein, we report the first use of sulfur-tethered dirhodium-(II,II) paddlewheel complexes in the detection of the nerve agent simulant DCP. Results show that Rh2(OAc)2(p-OMe-ArTCB)2 and Rh2(OAc)2(MeTCB)2 gave limits of detection (LODs) of 0.022 mM and 0.014 mM, respectively, by UV-vis. Though their LODs were similar, Rh2(OAc)2(MeTCB)2 showed better resistance to interferents. Spectroscopic studies provided new mechanistic insights that pointed to thioether donor abilities as the key factors for reactivity and interferent resistance. These results indicate that tethered complexes are robust toward interferents and can be tuned to improve selectivity and detection limits.
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