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Article Cite This: ACS Omega 2019, 4, 650−654
http://pubs.acs.org/journal/acsodf
Size Effect on Aurophilic Interaction in Gold-Chloride Cluster Anions of AunCln+1− (2 ≤ n ≤ 7) Yuan Ma,† Shen Bian,† Yingying Shi,† Xingting Fan,† and Xianglei Kong*,†,‡ †
The State Key Laboratory of Elemento-Organic Chemistry, Collage of Chemistry, and ‡Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071, China
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ABSTRACT: Aurophilic interaction plays a very important role in gold-related clusters. Here, we investigate the AunCln+1− (n = 1−7) cluster ions using Fourier transform ion cyclotron resonance mass spectrometry in combination with theoretical calculations. Three cluster ions of Au2Cl3−, Au3Cl4−, and Au4Cl5− show their remarkable intensities in the mass spectrum. Geometric structure optimizations for AunCln+1− (n = 1−7) were performed on the MP2 level. The results show that the most stable structures of AunCln+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 Au6Cl7− and Au7Cl8−, whereas the aurophilic interactions between nonterminal adjacent gold atoms stabilize at n = 5.
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INTRODUCTION Gold-containing compounds and clusters play an important role in the fields of catalysis,1−4 supramolecular chemistry,5 and material science.6,7 The chemical properties of gold clusters are affected by their structures as well as the interactions among Au atoms very much. In 1988, Schmidbaur first observed that the gold(I) molecule showed a short Au··· Au distance in the crystalline state.8,9 Furthermore, the term “aurophilicity” was formally proposed.10 Aurophilic interaction has an energy between those of van der Waals force and covalent bonding and plays an important role in stabilizing Au(I) compounds.11,12 Pyykkö and co-workers theoretically investigated the aurophilic interactions between closed shell Au(I) cationic centers over the past years.13−16 They suggested that the nature of aurophilic interactions can be understood as a dispersion effect. Among these related species, gold halides are found to be very useful in gold-catalyzed reactions.1,17−20 Thus, understanding their structures and properties have attracted a great amount of research in recent years.21−27 For example, Lemke investigated the microsolvated clusters of gold chloride by experiment and theoretical calculations.22 The results show that microsolvation enhances electron localization between Au centers. Li et al. systematically investigated the periodicity and electronic structures of gold tetrahalides [AuX4]− (X = F, Cl, Br, I, At, or Uus).23 Their results show that the Au(I) tends to be preferred for heavy halides. Wang et al. observed two types of isomers of Au2I3− with acute and obtuse Au−I−Au angles and named them bond-bending isomers (BBIs).25 Although the aurophilic interactions have been widely studied, investigation of the effect of cluster sizes on aurophilic interactions for gold-related clusters is rare. Because the sizes of clusters have a great impact on their structures, properties, and catalytic activities, this kind of research will be very © 2019 American Chemical Society
important and valuable. Here, we investigate clusters of AunCln+1− (n = 2−7) through Fourier transform ion cyclotron resonance (FT ICR) mass spectrometry combined with theoretical calculations. The present study focuses on the relationship between the size of gold-chloride cluster anions and the aurophilic interaction inside these clusters.
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RESULTS AND DISCUSSION A typical laser ablation mass spectrum of AuCl4H is shown in Figure 1. Cluster ions of AunCln+1− (n = 1−4), AunCln−1− (n = 2−4), and AunClnH− (n = 2−4) can be clearly identified in the mass spectrum. Among them, anions of Au2Cl3−, Au3Cl4− and Au4Cl5− show their remarkable intensities.
Figure 1. Laser ablation mass spectrum of AuCl4H obtained in the negative ion mode. Received: November 1, 2018 Accepted: December 28, 2018 Published: January 9, 2019 650
DOI: 10.1021/acsomega.8b02907 ACS Omega 2019, 4, 650−654
ACS Omega
Article
The structures of AunCln+1− (n = 1−7) cluster ions were examined through theoretical calculations. Figure 2 shows
Table 1 provides the main geometric parameters of the most stable structures. It can be found that the distances between adjacent gold atoms in Au2Cl3− and Au3Cl4− are 3.69, and 3.15 Å, respectively. For Au4Cl5−, the nonterminal and terminal Au−Au distances are 3.07 and 3.11 Å, respectively. Here, the terminal Au−Au distance is defined as the distance between the terminal gold atom and its adjacent gold atom; and the nonterminal Au−Au distance is defined as the distance between two inner adjacent gold atoms. These distances in Au3Cl4− and Au4Cl5− are shorter than the sum of the van der Waals radii of two Au atoms (3.32 Å), indicating the aurophilic attraction among Au atoms in the cluster ions. A comparison with these distances in AunCln+1− (n = 2−4) cluster ions shows that with the increase of Au atoms, the distances between adjacent gold atoms become shorter. In other words, the aurophilic interactions between adjacent gold atoms get stronger with the increase in the cluster size of AunCln+1− from n = 2−4. To better understand the relationship between the size of gold-chloride cluster ions and the aurophilic interaction, theoretical calculations were also performed for anions of Au5Cl6−, Au6Cl7−, and Au7Cl8− on the same level. As shown in Figure 3, the most stable structures of Au5Cl6−, Au6Cl7−, and
Figure 2. Some structures and their relative energies (ΔE, in kcal mol−1) of AunCln+1− (n = 1−4) cluster ions on the MP2 level.
some structures and the relative energies (ΔE) of AunCln+1− (n = 1−4) cluster ions on the MP2 level. As shown in the figure, the lowest energy geometry of AuCl2− has a linear form with a C2v symmetry, in which Au atom is in the middle of two Cl atoms. For Au2Cl3−, the most stable geometric structure is similar to the obtuse isomer of Au2I3− found by Wang et al.,25 and the Au−Au distance reported here is 3.69 Å. Interestingly, the most stable geometric structures of Au3Cl4− and Au4Cl5− are very similar. They are all characterized by a zigzag structure. The zigzag structures are found to be similar to those previously suggested or reported for some gold-related species.28−32 For example, previous study showed that the structure of AuCl crystals prepared by a vapor-transport method consisted of zigzag chains of Au and Cl with Au−Cl− Au bond angles of 92°.33,34 Other structures that also have some kinds of symmetry are found to be 10−70 kcal/mol higher in energies than the zigzag structures. All calculated vibrational frequencies for the most stable structures of AunCln+1− (n = 1−7) are shown in Table S1.
Figure 3. Most stable structures of (a) Au5Cl6−, (b) Au6Cl7−, and (c) Au7Cl8− found on the MP2 level.
Au7Cl8− are very similar in their structures. Remarkably, all of them are characterized by the zigzag structure. The terminal Au−Au distances in Au5Cl6−, Au6Cl7−, and Au8Cl7− are 3.08, 3.07, and 3.06 Å, respectively, which are slightly shorter than that in Au4Cl5− (3.11 Å). All nonterminal Au−Au distances in Au5Cl6−, Au6Cl7−, and Au8Cl7− stabilized at 3.06 Å. These results are also listed in Table 1. From this, it can be found that the more gold atoms in the clusters, the stronger the aurophilic interactions existed. This trend is prominent for small clusters (n ≤ 4) but inconspicuous for large ones (n > 4). For the aurophilic interaction between two nonterminal adjacent Au atoms, it stabilized more quickly than that between those
Table 1. Equilibrium MP2 Structural Parameters (with the Sets of ECP60MDF for Au and aug-cc-pVTZ for Cl) of AunCln+1− (n = 2−7); Bond Lengths are in Å and Angles are in Degreesa,b
