Superatomic Layer of Cubic Mo₄S₄ Clusters Connected by Cl Cross-Linking

Superatomic clusters - assemblies of atoms with various sizes, shapes, and compositions - can form hierarchical architectures that exhibit emergent electronic properties not found in their individual units. In particular, cubic M₄X₄ clusters of chalcogenides (M = transition metal; X = chalcogen) are recognized as versatile building blocks for 3D structures with tunable morphologies and electronic properties. However, tetrahedral M₄X₄ clusters rarely assemble into 2D architectures, which could offer a distinct class of functional materials from their 3D analogues. Here, this work reports the preparation of 2D Mo₈S₈Cl₁₁, a superatomic layer with a sandwich structure consisting of Mo₄S₄ clusters interconnected through Cl cross-linking. The vapor-phase reaction inside nanotubes promotes the selective growth of Mo₈S₈Cl₁₁ nanoribbons, allowing detailed characterization via transmission electron microscopy. This methodology can be applied to the growth of layered structures containing Mo₈S₈Cl₁₁ at the micrometer scale. This work has demonstrated that mono- and few-layer Mo₈S₈Cl₁₁ can be prepared by exfoliation of parent solids. Electronic structure calculations indicate that the 2D monolayer has quasi-flat bands, giving rise to an indirect-to-direct bandgap transition under mechanical strain. Furthermore, scanning electrochemical microscopy reveals the potential of the layered structures as highly efficient catalysts for the hydrogen-evolution reaction.