Polyoxometalate-Incorporated CuI-Resorcin[4]arene Metal-Organic Complexes as Heterogeneous Catalysts for Catalytic Oxidation of Mustard Gas Simulant

Exploring efficient heterogeneous catalysts for catalytic oxidation of chemical warfare agents (CWAs) is highly desired. As a class of discrete anionic metal oxide clusters, polyoxometalates (POMs) provide abundant catalytic active sites, thus resulting their rich redox properties. Here, a family of known POM-incorporated Cu^I-resorcin4]arene metal-organic complexes, namely, Cu₄(TPTR4A)₂]PW₁₂O₄₀](OH) ⋅ 0.5DMA ⋅ 5H₂O ( Cu - PW ), Cu₄(TPTR4 A)₂]PMo₁₂O₄₀](OH) ⋅ 2DMA ⋅ H₂O ( Cu - PMo ) and Cu₄(TPTR4A)₂]SiW₁₂O₄₀] ⋅ 2.5DMA ( Cu - SiW ) were utilized as catalysts to promote the oxidation of 2-chloroethyl ethyl sulfide (CEES). Strikingly, compared to the novel compound Cu₃Cl₆(TPTR4A)(DMA)] ⋅ CH₃CH₂OH (defined as Cu - T ), the three complexes exhibited excellent stability, indicating that the integration of POMs and metal–organic units could improve the stability of the compounds. Moreover, Cu - PMo and Cu - PW showed higher activities for the catalytic oxidation of CEES to CEESO with selectivities both of 99 %.