Aromatic Character of [Au13]5+ and [MAu12]4+/6+ (M = Pd, Pt) Cores in Ligand Protected Gold Nanoclusters – Interplay between Spherical and Planar σ-Aromatics

Authors

Nikita Fedik, Utah State UniversityFollow
Alexander I. Boldyrev, Utah State UniversityFollow
Alvaro Muñoz-Castro, Universidad Autonoma de Chile

Document Type

Article

Journal/Book Title

Physical Chemistry Chemical Physics

Publication Date

10-17-2019

Publisher

Royal Society of Chemistry

Award Number

NSF, Division of Chemistry (CHE) 1664379

Funder

NSF, Division of Chemistry (CHE)

Volume

21

Issue

45

First Page

1

Last Page

6

Related Content

Dobyrev, A. I., & Fedik, N. (2021). Data from: Aromatic character of [Au13]5+ and [MAu12]4+/6+(M = Pd, Pt) cores in ligand protected gold nanoclusters – interplay between spherical and planar sigma-aromatics. Utah State University. https://doi.org/10.26078/2MQ6-Q916

Abstract

The most characteristic feature of planar π-aromatics is the ability to sustain a long-range shielding cone under a magnetic field oriented in a specific direction. In this article, we showed that similar magnetic responses can be found in σ-aromatic and spherical aromatic systems. For [Au₁₃]⁵⁺, long-range characteristics of the induced magnetic field in the bare icosahedral core are revealed, which are also found in the ligand protected [Au₂₅(SH)₁₈]− model, proving its spherical aromatic properties, also supported by the AdNDP analysis. Such properties are given by the 8-ve of the structural core satisfying the Hirsch 2(N + 1)² rule, which is also found in the isoelectronic [M@Au₁₂]⁴⁺ core, a part of the [MAu₂₄(SR)₁₈]²⁻ (M = Pd, Pt) cluster. This contrasts with the [M@Au₁₂]⁶⁺ core in [MAu₂₄(SR)₁₈]⁰ (M = Pd, Pt), representing 6-ve superatoms, which exhibit characteristics of planar σ-aromatics. Our results support the spherical aromatic character of stable superatoms, whereas the 6-ve intermediate electron counts satisfy the 4N + 2 rule (applicable for both π- and σ-aromatics), showing the reversable and controlled interplay between 3D spherical and 2D σ-aromatic clusters.

Recommended Citation

Fedik, Nikita, et al. “Aromatic Character of [Au13]5+ and [MAu12]4+/6+ (M = Pd, Pt) Cores in Ligand Protected Gold Nanoclusters – Interplay between Spherical and Planar σ-Aromatics.” Physical Chemistry Chemical Physics, vol. 21, no. 45, The Royal Society of Chemistry, 2019, pp. 25215–19, doi:10.1039/C9CP04477A.