New structural insights into the stability of Au₂₂(SR)₁₆ nanocluster under ring model guidance

This study presents thorough structural insights into the stability of crystallized Au₂₂(SAdm)₁₆ (HSAdm = 1-adamantanethiol) nanocluster. With the recently developed Ring Model for describing the interaction between inner gold cores and outer protecting ligands in thiolate-protected gold nanoclusters, the experimental spontaneous transformation from the crystallized Au₂₂(SAdm)₁₆ to Au₂₁(SAdm)₁₅ could be well understood as structurally unfavorable for the current Au₂₂(SAdm)₁₆ and could also be attributed to the weaker aurophilic interaction between the inner Au₄ core and the surrounding rings in Au₂₂(SAdm)₁₆ over that in Au₂₁(SAdm)₁₅. Furthermore, with the Ring Model and the grand unified model, two new Au₂₂(SCH₃)₁₆ isomers with evident lower energies, higher HOMO-LUMO gaps as well as distinct optical properties over the available crystallized isomer were obtained. This study deepens the current knowledge on the structure of the Au₂₂(SR)₁₆ cluster from a new structural point of view and also confirms the validity as well as practicability of the Ring Model in understanding and predicting the stable structures of thiolate-protected gold nanoclusters.