Au₁₀(SG)₁₀: A Chiral Gold Catenane Nanocluster with Zero Confined Electrons. Optical Properties and First-Principles...

We report facile synthesis of the Au₁₀(SG)₁₀ nanoclusters, where SG stands for glutathione, found to be promising as a new class of radiosensitizers for cancer radiotherapy. The homoleptic catenane structure with two Au₅SG₅ interconnected rings, among different isomer structures, gives the best agreement between theoretical and experimental optical spectra and XRD patterns. This catenane structure exhibits a centrosymmetry-broken structure, resulting in enhanced second harmonic response and new characteristic circular dichroism signals in the spectral region of 250-400 nm. This is the first determination of the nonlinear optical properties of a ligated cluster with an equal Au-to-ligand ratio, thus without a metallic core and therefore zero confined electrons. Insight into the nonlinear and chiroptical efficiencies arising from interplay between structural and electronic properties is provided by the TD-DFT approach.