Diarsine- vs diphosphine-protected Au₁₃ clusters: Effect of subtle geometric differences on optical property and...

In the design of ligand-protected metal clusters, the choice of protecting ligands is a critical factor because they can profoundly affect the nuclearity, geometry, and electronic structures to afford a diverse range of cluster compounds. Here, we report the synthesis of two novel diarsine-protected Au₁₃ clusters ([Au₁₃L₅Cl₂]³⁺, L = diarsine) and compare these clusters with diphosphine analogs in terms of the core geometry and optical properties. In the crystal structure, the cluster bearing C3-bridged diarsines {[Au₁₃(dpap)₅Cl₂]³⁺, 3} had an apparently identical icosahedral Au₁₃ core to [Au₁₃(dppe)₅Cl₂]³⁺ (1) with C2-bridged diphosphines, but slight structural differences associated with the bridging unit of the ligands were found. Despite similar icosahedral Au₁₃ cores 1 and 3, their absorption and photoluminescence profiles were evidently different. Theoretical calculations revealed that the subtle deformation of the Au₁₃ icosahedron, rather than the coordinating atoms (As or P), notably influences the electronic structure to cause the difference in the absorption profiles.