Ligand-functionalized and ligand-bridged or organyl-separated chalcogenido metalate-based clusters

Chalcogenido metalate-based clusters, comprising cluster cores with directly bonded metal cations and chalcogenide anions, have been a focus of inorganic and materials research for decades, owing to their structural elegance and captivating catalytic-related and optical-related properties. The introduction of a ligand sphere to functionalize, bridge, or separate these clusters can help to stabilize and control the topology as well as chemical and physical properties of such compounds owing to interactions between clusters and ligands. In addition, this multiplied the product spectrum in the chalcogenido metalate-based cluster family. In this article, we give an overview of the recent developments of ligand-functionalized and ligand-bridged or organyl-separated chalcogenido metalate-based compounds. For this, we selected some prototypical cluster families, ranging from supertetrahedral clusters and cluster of related compositions but other structural motifs, to coinage metal clusters and compounds based on octahedral transition metal arrangements. By summarizing the research on these species, this review will provide a general overview of the syntheses and structures of selected contemporary ligand-functionalized and ligand-bridged or organyl-separated cluster compounds, contribute to understand the formation of the molecular structures and give some further insights into the effects of their functional modifications.