The structural isomerism in gold nanoclusters

Abstract

The isomerism in thiolate-protected gold (Au) nanoclusters is important for the understanding of structure–property correlations and the design of Au nanoclusters with specific structures and properties. Although recent studies have identified stereoisomerism, the understanding of structural isomerism is still lacking. Herein, we identified three distinct mechanisms of structural isomerism (i.e., core isomerism, staple isomerism, and complex isomerism) based on the crystallized isomers of thiolate-protected Au nanoclusters, and these mechanisms can be viewed as analogous to those of the structural isomerism in organic molecules (i.e., chain isomerism, point isomerism, and functional isomerism). Using the discovered core isomerism and staple isomerism, two Au₂₈(SR)₂₀ isomers are predicted and their synthesis feasibilities are illuminated. These new insights into the structural isomerism can facilitate rational design of new isomers of thiolate-protected Au nanoclusters and guide future experimental synthesis.