Synthesis of N₂-Type Superatomic Molecules.

Area of Science:

• * Inorganic Chemistry
• * Nanomaterials Science
• * Supramolecular Chemistry

Background:

• * The exploration of multiple bonding between superatoms is a nascent field.
• * Superatomic molecules offer unique properties distinct from conventional molecules.
• * Understanding the formation and characteristics of novel superatomic structures is crucial.

Purpose of the Study:

• * To synthesize and characterize nitrogen (N₂)-type superatomic molecules with triple bonds.
• * To investigate the formation mechanism of these novel superatomic structures.
• * To elucidate the electronic structure and properties of the synthesized superatomic molecules.

Main Methods:

• * Photoinduced fusion of MAu₁₂ superatoms to form M₂Au₁₇ nanoclusters (M = Pd, Pt).
• * Synthesis achieved through sequential electron transfer and detachment of [AuPR₃]⁺ species.
• * Characterization using X-ray crystallography for solid-state structures and Density Functional Theory (DFT) calculations for electronic structures.

Main Results:

• * Successful synthesis and structural confirmation of M₂Au₁₇ nanoclusters featuring superatomic triple bonds.
• * DFT calculations revealed detailed electronic structures of the superatomic molecules.
• * Analysis of electronic absorption properties showed symmetry-dependent electron transitions between superatomic molecular orbitals.

Conclusions:

• * The study demonstrates the feasibility of forming triple bonds between superatoms.
• * The electronic behavior of these superatomic triple bonds mimics that of conventional molecules.
• * This work expands the understanding of bonding in superatomic systems and opens possibilities for new materials.