Polyoxometalate-supported carbonyl metal derivatives: from synthetic strategies to structural diversity and applications.

Polyoxometalates (POMs) have demonstrated strong potential in various fields, such as catalysis, magnetism, medicine, photochemistry and materials science, mainly because of their remarkable physical and chemical properties. In the broad area of POM chemistry, the study of metal carbonyl-based POMs, as an important type of organometallic POMs, has been a rather attractive direction in recent years. POM-supported metal carbonyl derivatives (PMCDs), which utilize the advantages of both POMs and metal carbonyls, have emerged as a promising class of molecules, and much effort has been devoted to their preparation and relevant applications in the last decade. Thus far, substantial development of the synthetic chemistry of PMCDs by using one-pot synthesis has been reported mainly by us. This review focuses on different structural complexes, accompanied by Lindqvist-type, Keggin-type, Dawson-type, and nonclassical-type PMCDs, and is meant to provide fodder and guidance for further exploration and discovery of more intriguing PMCDs with innovative architectures and remarkable functionality. Herein, we highlight and discuss the structural features of PMCDs based on various structural types. Furthermore, synthetic strategies and relevant applications, especially in terms of photochemical properties and catalysis, are reviewed. Ideally, these concepts and strategies can be extended to other organometallic POMs.