Recent advances in single-crystal polyoxometalate-based metal–organic complex catalytic systems for sulfide–sulfoxide selective transformations

Abstract

The highly selective conversion of sulfides is of great significance for the synthesis of fine chemicals and bioactive pharmaceuticals and the prevention and control of environmental pollution. Catalytic oxidation technology provides an effective way to achieve this goal. However, the development of catalysts with both green characteristics and high selectivity is still a key challenge in this field. As a typical representative of environmentally friendly catalytic materials, single-crystal polyoxometalate-based metal–organic complexes (SC-POMOCs) show significant advantages due to their unique structural characteristics: (i) the synergistic effect between the redox activity of POM units and the structural tunability of MOCs creates an efficient catalytic microenvironment and (ii) the precise regulation of the spatial configuration of MOCs and POM units can effectively improve the activation efficiency of substrates. Research advances over the past decade have shown that such catalytic systems can achieve the efficient detoxification of chemical warfare agents and green synthesis of sulfoxide-containing drug molecules under mild conditions while exhibiting excellent cycling stability as heterogeneous catalysts. This review systematically summarizes the latest progress in SC-POMOCs for the selective oxidation of sulfides from the perspective of structural dimension and proposes the corresponding optimization strategies from the aspects of material design principles and catalytic technologies, aiming to provide theoretical foundations and technical support for constructing new-generation efficient catalytic platforms.