Diverse Superatomic Magnetic and Spin Properties of Au₁₄₄(SC₈H₉)₆₀Clusters

Au₁₄₄(SC₈H₉)₆₀, a colloidal cluster with a 1.7 nm inorganic diameter, exhibits both metallic and molecular-like behavior, along with a distribution of unfilled superatom states. Its 1.7–2.5 eV electronic transitions were probed with variable-temperature, variable-field magnetic circular dichroism (VTVH⇀[jls-end-space/]-MCD), revealing two energy regions with distinct responses. Below 2.0 eV, MCD transitions exhibited diverse VTVH⇀ responses, including both paramagnetic and diamagnetic behavior, implicating multiple nondegenerate initial states originating within the open-shell superatom S, D, and H HOMO manifold. Above 2.0 eV, uniform field-dependent responses suggested spin-vibronic coupling due to metal–ligand mixing. The Au₁₄₄(SC₈H₉)₆₀magneto-optical response is surprisingly complex given the system’s high electronic-state density; discrete structural domains of the cluster, including the superatomic metal core, likely contribute to this diversity. These results show the potential to investigate and tailor the magneto-optical and spin properties of these clusters through structurally precise synthesis and also identify superatomic colloids as candidates for advancing spin-based technologies.