Beyond The Sphere. Au₂₀(PR₃)₈ as a Spherical Aromatic Cuboctahedron Cluster

Area of Science:

• * Nanochemistry
• * Materials Science
• * Computational Chemistry

Background:

• * The icosahedral Au13 5+ core, with an 8-cluster electron shell (1S21P6), is a known building block in ligand-protected gold clusters, exhibiting spherical aromaticity and magnetic shielding.
• * Novel cuboctahedral gold clusters, such as Au20(tBu3P)8 with neutral gold atoms, present a new core architecture for functional nanostructures.

Purpose of the Study:

• * To investigate the ligand-core interaction and spherical aromatic characteristics of the Au20(tBu3P)8 cluster.
• * To establish a connection between cuboctahedral and icosahedral spherical aromatic gold compounds.
• * To rationalize the robustness of these clusters based on electron counts and aromaticity.

Main Methods:

• * Theoretical exploration of ligand-core interactions.
• * Analysis of electronic structure and aromatic properties.
• * Computational modeling of magnetic shielding effects.

Main Results:

• * The Au20(tBu3P)8 cluster displays spherical aromaticity, analogous to icosahedral clusters.
• * Its electronic structure supports a shielding cone property, contributing to cluster robustness.
• * A direct link between cuboctahedral and icosahedral spherical aromaticity in gold clusters is established.

Conclusions:

• * The cuboctahedral core in Au20(tBu3P)8 is a viable building block for functional nanostructures, exhibiting aromaticity.
• * Electron counts are crucial for the robustness and shielding properties of these metallic clusters.
• * This research unifies the concept of aromaticity across organic and inorganic species, providing design guidelines for future nanomaterials.