<i>In Situ</i> Organic Transformation Reactions Involved in Synthesis Process of Polyoxometalate‐Based Hybrids

Abstract The unique acidity, redox properties, and catalytic characteristics of polyoxometalates(POMs) provide an environment for the in situ transformation of organic molecules. The hydrothermal in situ ligand transformation has shown fascinating appeal in the synthesis of new POM‐based metal‐organic hybrid compounds due to its effectiveness, simplicity, and environmental friendliness. Currently, there has been an increasing number of reports on POM‐based metal‐organic hybrid compounds based on in situ transformation, and the study of the transformation mechanisms of organic components is of great significance for designing new POM‐based hybrid materials. Here, this review summarizes six types of in situ transformation reactions of organic molecules (pyrolysis, hydrolysis, oxidation, condensation, substitution, and cyclization), covering approximately forty kinds of organic molecules. The regulatory mechanisms during the in situ transformation process of organic molecules are discussed, and the impact of in situ transformed organic molecules on the structure of organic‐inorganic hybrid materials based on POMs is analyzed. The article also delves into the structure‐activity relationship between the in situ transformation of organic molecules and the properties of POM‐based composite materials. Finally, the article summarizes the existing problems in this field and provides an outlook on future development directions, aiming to showcase the broad application prospects in catalysis, materials science, energy, and medicinal chemistry.