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  • Accepted Manuscript: Aromatic character of [Au 13 ] 5+ and [MAu 12 ] 4+/6+ (M = Pd, Pt) cores in ligand protected gold nanoclusters – interplay between spherical and planar σ-aromatics
Title: Aromatic character of [Au 13 ] 5+ and [MAu 12 ] 4+/6+ (M = Pd, Pt) cores in ligand protected gold nanoclusters – interplay between spherical and planar σ-aromatics
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 [Au 13 ] 5+ , long-range characteristics of the induced magnetic field in the bare icosahedral core are revealed, which are also found in the ligand protected [Au 25 (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@Au 12 ] 4+ core, a part of the [MAu 24 (SR) 18 ] 2− (M = Pd, Pt) cluster. This contrasts with the [M@Au 12 ] 6+ core in [MAu 24 (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 4 N + 2 rule (applicable for both π- and σ-aromatics), showing the reversable and controlled interplay more » between 3D spherical and 2D σ-aromatic clusters. « less
Authors:
; ;
Award ID(s):
1664379
Publication Date:
NSF-PAR ID:
10196542
Journal Name:
Physical Chemistry Chemical Physics
Volume:
21
Issue:
45
Page Range or eLocation-ID:
25215 to 25219
ISSN:
1463-9076
Sponsoring Org:
National Science Foundation
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