Synthesis of N 2 -Type Superatomic Molecules.

Exploration of multiple bonds between superatoms remains an uncharted territory. In this study, we present the synthesis and characterization of N ₂ -type superatomic molecules featuring triple bonds between two superatoms. The successful synthesis of M ₂ Au ₁₇ (M = Pd, Pt) nanoclusters hinged upon the photoinduced fusion of MAu ₁₂ superatoms, achieved through sequential electron transfer and detachment of [AuPR ₃ ] ⁺ species. Solid-state structures were confirmed via X-ray crystallography, while their electronic structures were elucidated through density functional theory (DFT) calculations. Analysis of electronic absorption properties, coupled with time-dependent DFT calculations, unveiled a symmetry-dependent electron transition nature between superatomic molecular orbitals, akin to that observed in conventional molecules.