Two Tetra-Nuclear Ln-Substituted Prazine Dicarboxylic Acid-Functionalized Selenotungstates with Catalytic Oxidation of Thioether Properties.

Abstract

Two two-dimensional Ln-substituted prazine dicarboxylic acid-functionalized selenotungstates Na3H9[(H2N(CH3)2]2{(Se4W27O100)[Ln4(H2O)8(Hpzdc)2(pzdc)]}·26H2O [Ln = Nd (1) and Ce (2)]; H2pzdc = 2,3-pyrazine dicarboxylic acid) have been synthesized by one-pot self-assembly strategy, in which the basic polyanion [Se4W27O100]22-was composed of two [SeW8O31]10- fragments, a [SeW9O33]8- segment and an intriguing {SeO} group, simultaneously tetra-nuclear Ln3+ ions with H2pzdc pendants were embedded. Compounds 1 and 2 showed excellent catalytic oxidation of thioether properties within a short time (20 min) with high 100% conversion and 98.9% selectivity. In addition, the pioneering Ln-substituted selenotungstates were used as catalysts to degrade sulfur mustard simulant 2-chloroethyl ethyl sulfide at room temperature with 99% conversion and 100% selectivity. The chemical kinetic experiment studies revealed that the catalytic reaction was in compliance with the first-order reaction, and the kinetic half-life (t1/2) values were 3.814 and 3.849 min, respectively.