Size Effect on Aurophilic Interaction in Gold-Chloride Cluster Anions of Au_nCl_n+1^– (2 ≤ n ≤ 7)

Abstract

Aurophilic interaction plays a very important role in gold-related clusters. Here, we investigate the Au n Cl n +1 – ( n = 1–7) cluster ions using Fourier transform ion cyclotron resonance mass spectrometry in combination with theoretical calculations. Three cluster ions of Au 2 Cl 3 – , Au 3 Cl 4 – , and Au 4 Cl 5 – show their remarkable intensities in the mass spectrum. Geometric structure optimizations for Au n Cl n +1 – ( n = 1–7) were performed on the MP2 level. The results show that the most stable structures of Au n Cl n +1 – ( n = 2–7) are all characterized by a zigzag structure. Furthermore, it can be found that the aurophilic interactions containing terminal gold atoms strengthen with the increase of total gold atoms and progressively stabilize for large clusters of Au 6 Cl 7 – and Au 7 Cl 8 – , whereas the aurophilic interactions between nonterminal adjacent gold atoms stabilize at n = 5.

Reaction of chloroauric acid with histidine in microdroplets yields a catalytic Au–(His)2complex

“… 55 This strong electric field formed at the air–water interface is expected to promote the reduction of AuCl 4 − to Au in which gold goes from the +3 valence state to zero. 56 The source of the electrons causing this reduction is believed to be from the OH − anion. 18 Fig.…”

“…to Au in which gold goes from the +3 valence state to zero. 56 The source of the electrons causing this reduction is believed to be from the OH À anion. 18 Fig.…”

Excimer and Exciplex Formation in Gold(I) Complexes Preconditioned by Aurophilic Interactions

“…The anion is to be taken as an example of a molecule oscillating between different structures as a result of two competing chemical forces, as also supported by quantum‐chemical calculations . Larger [(AuCl) n Cl] − anions have been assigned a zigzag structure with a central chain of gold atoms resembling that in crystals of AuCl …”

“…[156] Larger [(AuCl) n Cl] À anions have been assigned az igzag structure with ac entral chain of gold atoms resembling that in crystals of AuCl. [157] UV/Vis absorption and emission properties have been the main focus of studies of transannular Au•••Aui nteractions. [17,[158][159][160] Typical examples have been the eight-membered-ring complexes of 1,3-difunctional phosphines where two roughly parallel P-Au-P axes are held in close proximity (N).…”

Excimer‐ und Exciplex‐Bildung in durch aurophile Wechselwirkungen präkonditionierten Gold(I)‐ Komplexen

“…Dieses Anion ist ein Beispiel für ein Molekül, welches aufgrund zweier konkurrierender chemischer Kräfte zwischen verschiedenen Strukturen oszilliert, was auch durch quantenchemische Berechnungen gestützt wird . Größeren Anionen [(AuCl) n Cl] − wurden Zickzack‐Strukturen mit einer zentralen Kette aus Goldatomen zugewiesen, ähnlich der, die in Kristallen von AuCl gefunden werden …”