Pd and Hg Atoms Co-doped HgPdAu23(PET)18 Nanocluster★

doi:10.6023/A23030078

Abstract

The introduction of heteroatoms into metal nanoclusters is an effective strategy to regulate the physical and chemical properties of clusters. Most of the doped clusters reported are binary metal nanoclusters via one metal heteroatom doping into a metal nanocluster, while the preparation and properties of ternary metal nanoclusters via two heteroatoms doping into a metal nanocluster are rarely studied. In this work, we report the Pd and Hg co-doped ternary metal nanocluster HgPdAu₂₃(PET)₁₈(PET=2-phenylethanethiol) using the Au₂₅(PET)₁₈ nanocluster as an ideal template that can be viewed as a Au₁₃ icosahedral core protected by the exterior 12 Au atoms as a shell. The structural framework of the HgPdAu₂₃(PET)₁₈ nanocluster is similar to that of its parent Au₂₅(PET)₁₈ nanocluster, determined by single-crystal X-ray crystallography and electrospray ionization mass spectroscopy (ESI-MS), which shows a 13-atom icosahedral core and a 12-atom shell capped by 18 thiolate ligands. It indicated that the doping strategy might destroy the total structure (core plus surface) of the parent nanocluster, which will offer an excited opportunity for the correlation of the structure with properties of the doped nanoclusters. More notably, the possible doping location of the Pd and Hg atoms in the HgPdAu₂₃(PET)₁₈ nanocluster can be determined by the combination of single-crystal X-ray crystallography and nuclear magnetic resonance (NMR) spectroscopy (i.e., ¹H NMR and two-dimentional NMR). It is suggested that the Pd atom is possibly located on the center of the icosahedron of the HgPdAu₂₃(PET)₁₈ nanocluster, while the Hg atom is possibly located on the surface of the icosahedron of the HgPdAu₂₃(PET)₁₈ nanocluster. The electronic configuration of HgPdAu₂₃(PET)₁₈ nanocluster is distinct from those of the parent Au₂₅(PET)₁₈ and one-metal doped PdAu₂₄(PET)₁₈ and HgAu₂₄(PET)₁₈ nanoclusters, which can be implied by the X-ray photoelectron spectroscopy (XPS) and UV-Vis absorption spectroscopy. This study provides a new design rule for the two-metal-heteroatom doped nanoclusters.

Key words: nanocluster, heteroatoms, doping, structure

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Yuying Zhang, Xiao Cai, Weigang Hu, Guangjun Li, Yan Zhu. Pd and Hg Atoms Co-doped HgPdAu₂₃(PET)₁₈ Nanocluster^★[J]. Acta Chimica Sinica, 2023, 81(7): 703-708.

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Fig. & Tab. 7

Figure 1. (a) Electrospray mass data of HgPdAu23(PET)18 cluster; (b) Au 4f XPS spectra of Au25(PET)18, PdAu24(PET)18, HgAu24(PET)18 and HgPdAu23(PET)18; (c) Pd 3d XPS spectra of PdAu24(PET)18 and HgPdAu23(PET)18; (d) XPS Hg 4f spectra of HgAu24(PET)18 and HgPdAu23(PET)18

Figure 2. Crystal structures of Au25(PET)18, PdAu24(PET)18, HgAu24(PET)18 and HgPdAu23(PET)18 nanoclusters (Color code: green=Au, magenta=Pd, blue=Hg, yellow=sulfur; C and H atoms are omitted)

Figure 3. 1H NMR spectra of HgAu24(PET)18 and HgPdAu23(PET)18 clusters in the range of δ 2.80~3.80

Figure 4. Two-dimensional NMR spectra (H-H COSY) of HgPdAu23(PET)18 cluster

Figure 5. Two-dimensional NMR spectra (HMQC) of HgPdAu23(PET)18 cluster

	[Au₂₅]^－	[PdAu₂₄]⁰	[HgAu₂₄]⁰	[HgPdAu₂₃]⁰
M_core—M_shell/nm	0.2759~0.2789	0.2738~0.2798	0.2779~0.2805	0.2771~0.2796
Averaged value/nm	0.2774	0.2778	0.2792	0.2781
SD^a/nm	0.0011	0.0023	0.0010	0.0008
M_shell—M_shell/nm	0.2789~0.2947	0.2745~0.3223	0.2810~0.3023	0.2792~0.3013
Averaged value/nm	0.2918	0.2921	0.2937	0.2925
SD/nm	0.0063	0.0163	0.0071	0.0072

Table 1. Crystal structure parameters of Au25(PET)18, PdAu24(PET)18, HgAu24(PET)18 and HgPdAu23(PET)18 clusters

Figure 6. UV-Vis spectra of (a) Au25, (b) PdAu24, (c) HgAu24 and (d) HgPdAu23 clusters

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Pd和Hg共掺杂的金属纳米团簇HgPdAu₂₃(PET)₁₈^★

Pd and Hg Atoms Co-doped HgPdAu₂₃(PET)₁₈ Nanocluster^★

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Pd和Hg共掺杂的金属纳米团簇HgPdAu23(PET)18★