Recent advances in polyoxometalate-templated high-nuclear silver clusters

• The developments of POM-templated silver clusters are reviewed. • The syntheses, structures, properties and applications of POM-templated silver clusters are summarized. • The structure–property/application relationships of POM-templated silver clusters are discussed. • The development prospects and the current challenges for POM-templated silver clusters are discussed. • The suggestions for the further development of POM-templated silver clusters are presented. The search for feasible strategies to construct high-nuclear silver clusters has been attracting continuous interests because such materials not only exhibit aesthetic structures and fascinating properties, but also show promising applications in photoluminescence, antibiosis materials, photochromism, nano-materials, and electron transfer/communication materials. Anions are well-known as templates to direct the formation of silver clusters and control the shapes, sizes, and functions of the final products. As a unique class of anionic metal-oxo species, polyoxometalates (POMs) have been widely employed as templates in the syntheses of many intriguing silver clusters. In this review, the advances in POM-templated high-nuclear silver clusters in the past decade are summarized. Additionally, the different templating effects between POMs and simple inorganic anions are discussed. Actually, POMs can do much more than templates for the formation of diverse high-nuclear silver architectures, they also are significant in stabilizing the final products, functionalizing the composite clusters, and so on. Based on the current development in this area, the present challenges and perspectives for such materials are also presented. We hope that this review will be of reference value to accelerate the further development of silver clusters.