Interplay of Charge State, Lability, and Magnetism in the Molecule-like Au₂₅(SR)₁₈ Cluster

Abstract

Au₂₅(SR)₁₈ (R = −CH₂–CH₂–Ph) is a molecule-like nanocluster displaying distinct electrochemical and optical features. Although it is often taken as an example of a particularly well-understood cluster, very recent literature has provided a quite unclear or even a controversial description of its properties. We prepared monodisperse Au₂₅(SR)₁₈⁰ and studied by cyclic voltammetry, under particularly controlled conditions, the kinetics of its reduction or oxidation to a series of charge states, −2, −1, +1, +2, and +3. For each electrode process, we determined the standard heterogeneous electron-transfer (ET) rate constants and the reorganization energies. The latter points to a relatively large inner reorganization. Reduction to form Au₂₅(SR)₁₈^2– and oxidation to form Au₂₅(SR)₁₈²⁺ and Au₂₅(SR)₁₈³⁺ are chemically irreversible. The corresponding decay rate constants and lifetimes are incompatible with interpretations of very recent literature reports. The problem of how ET affects the Au₂₅ magnetism was addressed by comparing the continuous-wave electron paramagnetic resonance (cw-EPR) behaviors of radical Au₂₅(SR)₁₈⁰ and its oxidation product, Au₂₅(SR)₁₈⁺. As opposed to recent experimental and computational results, our study provides compelling evidence that the latter is a diamagnetic species. The DFT-computed optical absorption spectra and density of states of the −1, 0, and +1 charge states nicely reproduced the experimentally estimated dependence of the HOMO–LUMO energy gap on the actual charge carried by the cluster. The conclusions about the magnetism of the 0 and +1 charge states were also reproduced, stressing that the three HOMOs are not virtually degenerate as routinely assumed: In particular, the splitting of the HOMO manifold in the cation species is severe, suggesting that the usefulness of the superatom interpretation is limited. The electrochemical, EPR, and computational results thus provide a self-consistent picture of the properties of Au₂₅(SR)₁₈ as a function of its charge state and may furnish a methodology blueprint for understanding the redox and magnetic behaviors of similar molecule-like gold nanoclusters