A construction guide for high-nuclearity (≥50 metal atoms) coinage metal clusters at the nanoscale: bridging molecular precise constructs with the bulk material phase.

Synthesis remains a major strength in chemistry and materials science and relies on the formation of new molecules and diverse forms of matter. The construction and identification of large molecules poses specific challenges and has historically lain in the realm of biological (organic)-type molecules with evolved synthesis methods to support such endeavours. But with the development of analytical tools such as X-ray crystallography, new synthesis methods toward large metal-based (inorganic) molecules and clusters have come to the fore, making it possible to accurately determine the precise distribution of hundreds of atoms in large clusters. In this review, we focus on different synthesis protocols used to form new metal clusters such as templating, alloying and size-focusing strategies. A specific focus is on group 11 metals (Cu, Ag, Au) as they currently predominate large metal cluster investigations and related Au and Ag bulk surface phenomena. This review focuses on metal clusters that have very high-nuclearity, i.e. with 50 or more metal centers within the isolated cluster. This size domain, it is believed, will become increasingly important for a variety of applications as these metal clusters are positioned at the interface between the molecular and bulk phases, whilst remaining a classic nanomaterial and retaining unique nano-sized properties.