In this work, we illustrated the design and development of a metal-coordinated porous organic polymer (POP) namely VO@TPA-POP via a post-synthetic metalation strategy to incorporate oxo-vanadium sites in a pristine polymer (TPA-POP) having acetylacetonate (acac) as anchoring moiety. The as-synthesized VO@TPA-POP exhibited highly robust and porous framework, which has been utilized for thioanisole (TA) oxidation to its corresponding sulfoxide. The catalyst demonstrated notable stability and recyclability by maintaining its catalytic activity over multiple reaction cycles without any significant loss in activity. The X-ray absorption spectroscopy (XAS) and density functional theory (DFT) analysis establish the existence of V(+4) oxidation state along with the VO(O)₄ active sites into the porous network and the most energetically feasible mechanistic pathway involved in the TA oxidation, respectively, indicating the role of electron density associated with vanadium center during the catalytic transformation. Thus, this work aims at the demonstration of versatility and potential of VO@TPA-POP as a porous heterogeneous catalyst for the TA oxidation followed by decontamination of sulfur mustards (HD’s) to their corresponding less toxic sulfoxides in a more efficient and greener way.

中文翻译：

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捕捉氧化钒酸盐多孔乙酰丙酮共价自适应催化网络，使芥子气模拟物无害

在这项工作中，我们阐述了金属配位多孔有机聚合物（POP）即VO@TPA-POP的设计和开发 ，通过后合成金属化策略将氧钒位点纳入原始聚合物（TPA-POP）中，乙酰丙酮酸（acac）作为锚定部分。合成的VO@TPA-POP表现出高度稳健的多孔框架，可用于将茴香硫醚 (TA) 氧化为其相应的亚砜。该催化剂通过在多个反应循环中保持其催化活性而没有任何显着的活性损失，表现出显着的稳定性和可回收性。 X 射线吸收光谱 (XAS) 和密度泛函理论 (DFT) 分析确定了 V(+4) 氧化态以及 VO(O) ₄活性位点进入多孔网络的存在以及所涉及的最能量可行的机制途径分别在TA氧化中，表明了催化转化过程中与钒中心相关的电子密度的作用。因此，这项工作旨在展示VO@TPA-POP作为 TA 氧化的多孔多相催化剂的多功能性和潜力，然后以更有效和更环保的方式将硫芥（HD）净化为其相应的毒性较小的亚砜。