Template synthesis of discrete metal clusters with two- or three-dimensional architectures

Discrete transition-metal clusters with metal-metal or metal-oxygen-metal bonds represent a new cat-egory of functional materials with numerous unusual properties. For instance, the availability of multiple coordination sites on account of the presence of multiple metal atoms in the metal clusters contributes to cooperative interactions, endowing such clusters with more specific or superior catalytic activity com-pared to mononuclear complexes or bulk metals. The properties of transition-metal clusters depend on the structural parameters of the clusters, including the number of metal atoms and the overall structural geometry of the cluster. However, conventional synthetic methods for metal clusters, e.g., self-assembly or the reductive assembly of metal species, usually offer only poor control over such structural parame-ters. In this review, we focus on a recently introduced strategy for the synthesis of metal clusters that can overcome the aforementioned drawbacks, namely, the template synthesis of metal clusters, in which well-designed template molecules such as polyoxometalates, multidentate nitrogen-or phosphine-based ligands, or unsaturated hydrocarbons serve as effective multidentate ligands to construct two -or three-dimensional metal clusters in a highly selective manner. In addition, the precise assembly of multiple metal atoms with the aid of oligosilanes through the sequential insertion of metal species into Si-Si bonds will be discussed. (c) 2022 Elsevier B.V. All rights reserved.

Automated summary

Discrete transition-metal clusters with metal-metal or metal-oxygen-metal bonds are a new category of functional materials with unique properties. The synthesis of these clusters using template molecules allows for better control over the structural parameters, leading to more specific and superior catalytic activity.