Rapid Oxidative Detoxification of Mustard Simulant by the Multisite Synergistic Catalytic Action of {PMo VI 11 Mo V O 40 Cu I 8 } Units.

Under hydrothermal and solvent-thermal conditions, we synthesized two novel polyoxometalate (POM)-based hybrids: [Cu I 4 (Pz) 2 (H 2 O) 8 (PMo VI 11 Mo V O 40 )]·3.5H 2 O ( 1 , Pz = pyrazine) and [(C 2 H 8 N) 5 (HPMo VI 9 Mo V 3 O 40) ] · DMF · 4H 2 O ( 2 ). Single-crystal X-ray diffraction indicates that compound 1 is a three-dimensional structure consisting of Cu (I), {PMo 12 } anions, Pz, and water, where Cu (I) can be considered as Lewis acid sites. Furthermore, both compounds 1 and 2 possess favorable catalysis activity in catalyzing the conversion of chemical warfare agent simulant 2-chloroethylethyl sulfide (CEES) to nontoxic production of 2-chloroethylethyl sulfoxide (CEESO) under ambient temperature. Significantly, 1 could realize 98% conversion and 100% selectivity of CEES owing to the multisite synergy in the {PMo VI 11 Mo V O 40 Cu I 8 } units in which the tricoordinated Cu (I) could interact with S and O atoms from CEES and H 2 O 2 , respectively. This interaction not only decreases the distance of CEES from peroxomolybdenum species formed by H 2 O 2 but also activates CEES.