Synthesis of N2-Type Superatomic Molecules.

Abstract

Exploration of multiple bonds between superatoms remains an uncharted territory. In this study, we present the synthesis and characterization of N₂-type superatomic molecules featuring triple bonds between two superatoms. The successful synthesis of M₂Au₁₇ (M = Pd, Pt) nanoclusters hinged upon the photoinduced fusion of MAu₁₂ superatoms, achieved through sequential electron transfer and detachment of [AuPR₃]⁺ 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.