Intermediate Intercluster Bond Orders. Electronic Communication in Au 38 (SR) 24 Superatomic Molecules

Ligand-protected gold clusters remain potential building blocks for envisaged molecular materials. The archetypal Au (SR) cluster can be viewed as a robust template for the fusion of two Au (SR) cluster units, retaining a bi-icosahedral Au core. Via electrochemical properties, the overall charge state can be selectively tuned, enabling the access of 14 valence electron (ve) species featuring a single intercluster bond and nearby charge from -1 to +3, achieving related species bearing 15- to 11-ve with variable intercluster bond orders. Here, we explore the characteristics of intermediate intercluster bond orders in order to provide insights into the plausible electron communication between the constituent building blocks, with Au (SR) , as a representative template. Our results denote a small structural variation along -1 to +3 charge states, provided by the core-protecting ligand interaction, which is enhanced towards more oxidized species. The remaining unpaired electron from intermediate intercluster bond orders of 1.5 for Au (SR) , 1.5 for Au (SR) , and 2.5 for Au (SR) , holds delocalized characteristics between the building block units, favoring electron communication for conductive and cooperative cluster aggregates. Such features are relevant for the formation of molecular electronic device applications, favoring the rationalization prior to engaging in explorative synthesis of larger ligand-protected cluster aggregates.