Thiolate-Protected Bimetallic Nanoclusters: Understanding the Relationship between Electronic and Catalytic...

Thiolate-protected metal nanoclusters, which are smaller than 2 nm and have a specific number of metal atoms, have been greatly investigated in areas such as catalysis, sensing, and energy conversion because of their unique chemical, optical, structural, and electronic properties. Doping monometallic nanoclusters with another metal offers the opportunity to enhance these properties even further. The atomic structure of thiolate-protected bimetallic nanoclusters has been thoroughly studied using various X-ray methods, but the electronic structures of these complexes are often under-discussed. This Perspective summarizes works examining the electronic properties (charge states and energy levels) of these materials using density functional theory, square-wave voltammetry, UV-vis spectroscopy, and X-ray photoelectron spectroscopy. This information is then related to the catalytic activities of these complexes in various representative reactions (e.g., carbon-carbon coupling, hydrogenation, and oxidation). The significance of the structure-property relationship between the electronic properties and the catalytic performance of thiolate-protected bimetallic nanoclusters is demonstrated.