Sulfur-PassivatedSuperatomic Rh13S8± Clusterswith Enhanced Stability and UniqueElectronic Properties

Abstract

Abstract Metal sulfides have attracted considerable attention in nanomaterials because of their unique properties supporting key applications in catalysis, energy storage, sensing and others. Thiol-protected metal clusters feature similar metal–sulfur bonding as in nanomaterials, but the underlying formation mechanism and structure–property relationships remain not fully understood. In this work, we prepared pure rhodium clusters and studied their reactivity with H2S. Intriguingly, a novel sulfide cluster Rh13S8± consistently emerged from the gas-phase reactions. Relativistic quantum chemistry studies revealed a perovskite-like cubic structure composed of eight Rh3S units, featuring multicenter bonds and distinctive intracluster μ3-S interactions of Rh@Rh12S8±. Analysis of valence electron configurations elucidates how localized and delocalized electrons dictate its exceptional stability and cubic aromaticity. The unique stability and properties render this cluster a promising candidate for developing metal–sulfide materials with hyperpolarizability.