Next Article in Journal
Nanostructuration of Thin Metal Films by Pulsed Laser Irradiations: A Review
Next Article in Special Issue
In Situ Decoration of Gold Nanoparticles on Graphene Oxide via Nanosecond Laser Ablation for Remarkable Chemical Sensing and Catalysis
Previous Article in Journal
Interaction of Gold Nanorods with Human Dermal Fibroblasts: Cytotoxicity, Cellular Uptake, and Wound Healing
Previous Article in Special Issue
Gold Nanoclusters: Bridging Gold Complexes and Plasmonic Nanoparticles in Photophysical Properties
Open AccessArticle

New Perspectives on the Electronic and Geometric Structure of Au70S20(PPh3)12 Cluster: Superatomic-Network Core Protected by Novel Au123-S)10 Staple Motifs

by 1,2, 3 and 1,4,*
1
Department of Chemistry, Anhui University, Hefei 230601, China
2
School of Chemistry and Materials Engineering, Fuyang Normal University, Fuyang 236037, China
3
School of Social and Public Administration, East China University of Science and Technology, Shanghai 200237, China
4
Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University, Hefei 230601, China
*
Author to whom correspondence should be addressed.
Nanomaterials 2019, 9(8), 1132; https://doi.org/10.3390/nano9081132
Received: 5 July 2019 / Revised: 26 July 2019 / Accepted: 30 July 2019 / Published: 6 August 2019
In order to increase the understanding of the recently synthesized Au70S20(PPh3)12 cluster, we used the divide and protect concept and superatom network model (SAN) to study the electronic and geometric of the cluster. According to the experimental coordinates of the cluster, the study of Au70S20(PPh3)12 cluster was carried out using density functional theory calculations. Based on the superatom complex (SAC) model, the number of the valence electrons of the cluster is 30. It is not the number of valence electrons satisfied for a magic cluster. According to the concept of divide and protect, Au70S20(PPh3)12 cluster can be viewed as Au-core protected by various staple motifs. On the basis of SAN model, the Au-core is composed of a union of 2e-superatoms, and 2e-superatoms can be Au3, Au4, Au5, or Au6. Au70S20(PPh3)12 cluster should contain fifteen 2e-superatoms on the basis of SAN model. On analyzing the chemical bonding features of Au70S20(PPh3)12, we showed that the electronic structure of it has a network of fifteen 2e-superatoms, abbreviated as 15 × 2e SAN. On the basis of the divide and protect concept, Au70S20(PPh3)12 cluster can be viewed as Au4616+[Au123-S)108−]2[PPh3]12. The Au4616+ core is composed of one Au2212+ innermost core and ten surrounding 2e-Au4 superatoms. The Au2212+ innermost core can either be viewed as a network of five 2e-Au6 superatoms, or be considered as a 10e-superatomic molecule. This new segmentation method can properly explain the structure and stability of Au70S20(PPh3)12 cluster. A novel extended staple motif [Au123-S)10]8− was discovered, which is a half-cage with ten µ3-S units and six teeth. The six teeth staple motif enriches the family of staple motifs in ligand-protected Au clusters. Au70S20(PPh3)12 cluster derives its stability from SAN model and aurophilic interactions. Inspired by the half-cage motif, we design three core-in-cage clusters with cage staple motifs, Cu6@Au123-S)8, Ag6@Au123-S)8 and Au6@Au123-S)8, which exhibit high thermostability and may be synthesized in future. View Full-Text
Keywords: Au70S20(PPh3)12 cluster; superatom network model; electronic structure; geometric structure Au70S20(PPh3)12 cluster; superatom network model; electronic structure; geometric structure
Show Figures

Figure 1

MDPI and ACS Style

Tian, Z.; Xu, Y.; Cheng, L. New Perspectives on the Electronic and Geometric Structure of Au70S20(PPh3)12 Cluster: Superatomic-Network Core Protected by Novel Au123-S)10 Staple Motifs. Nanomaterials 2019, 9, 1132.

Show more citation formats Show less citations formats
Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Article Access Map

1
Back to TopTop