Au70S20(PPh3)12 as Superatomic Analog to 18‐electron Transition‐Metal Complexes

Muñoz-Castro, Álvaro

doi:10.1002/zaac.202100134

Cited by 3 publications

(1 citation statement)

References 77 publications

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“…Expanding the proposed elementary blocks, Muñoz-Castro described the 18-electron Au 22 4+ core of the Au 70 S 20 (PPh 3 ) 12 cluster as a tetrahedral aggregation of Au 6 units. [188] Modifying the electronic structure of the Au clusters can be achieved by doping with different metal atoms. The effect of doping with lower valent atoms, such as Pt, Pd, and Ni, at the central position of the icosahedral core of Au 13 results in the reduction of the effective potential, which then causes destabilization of the superatomic orbitals (SOs).…”

Section: Electronic Structuresmentioning

confidence: 99%

A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

et al. 2022

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Atomically precise gold clusters are highly desirable due to their well-defined structure which allows the study of structure-property relationships. In addition, they have potential in technological applications such as nanoscale catalysis. The structural, chemical, electronic, and optical properties of ligated gold clusters are strongly defined by the metal-ligand interaction and type of ligands. This critical feature renders gold-phosphine clusters unique and distinct from other ligand-protected gold clusters. The use of multidentate phosphines enables preparation of varying core sizes and exotic structures beyond regular polyhedrons. Weak gold-phosphorous (Au-P) bonding is advantageous for ligand exchange and removal for specific applications, such as catalysis, without agglomeration. The aim of this review is to provide a unified view of gold-phosphine clusters and to present an in-depth discussion on recent advances and key developments for these clusters. This review features the unique chemistry, structural, electronic, and optical properties of gold-phosphine clusters. Advanced characterization techniques, including synchrotron-based spectroscopy, have unraveled substantial effects of Au-P interaction on the composition-, structure-, and size-dependent properties. State-of-the-art theoretical calculations that reveal insights into experimental findings are also discussed. Finally, a discussion of the application of gold-phosphine clusters in catalysis is presented.

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Section: Electronic Structuresmentioning

confidence: 99%

A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

et al. 2022

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Tri- and Tetra-superatomic Molecules in Ligand-Protected Face-Fused Icosahedral (M@Au₁₂)_n (M = Au, Pt, Ir, and Os, and n = 3 and 4) Clusters

Zhou

et al. 2022

J. Phys. Chem. Lett.

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Cluster assembling has been one of the hottest topics in nanochemistry. In certain ligand-protected gold clusters, bi-icosahedral cores assembled from Au 13 superatoms were found to be analogues of diatomic molecules F 2 , N 2 , and singlet O 2 , respectively, in electronic shells, depending upon the super valence bond (SVB) model. However, challenges still remain for extending the scale in cluster assembling via the SVB model. In this work, ligand-protected tri-and tetra-superatomic clusters composed of icosahedral M@Au 12 (M = Au, Pt, Ir, and Os) units are theoretically predicted. These clusters are stable with reasonable highest occupied molecular orbital (HOMO)−lowest unoccupied molecular orbital (LUMO) energy gaps and proven to be analogues of simple triatomic (Cl 3 − , OCl 2 , O 3 , and CO 2 ) and tetra-atomic (NC−CN, and Cl−CC−Cl) molecules in both geometric and electronic structures. Moreover, a stable clusterassembling gold nanowire is predicted following the same rules. This work provides effective electronic rules for cluster assembling on a larger scale and gives references for their experimental synthesis.

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Assembling Au₄ Tetrahedra to 2D and 3D Superatomic Crystals Based on Superatomic-Network Model

Chen

Wang

et al. 2022

ACS Omega

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Thiolate-protected gold nanoclusters (denoted as Au m (SR) n or Au n L m ) have received extensive attention both experimentally and theoretically. Understanding the growth mode of the Au 4 unit in Au m (SR) n is of great significance for experimental synthesis and the search for new gold clusters. In this work, we first build six clusters of Au 7 (AuCl 2 ) 3 , Au 12 (AuCl 2 ) 4 , Au 16 (AuCl 2 ) 6 , Au 22 (AuCl 2 ) 6 , and Au 30 (AuCl 2 ) 6 with the Au 4 unit as the basic building blocks. Density functional theory (DFT) calculations show that these newly designed clusters have high structural and electronic stabilities. Based on chemical bonding analysis, the electronic structures of these clusters follow the superatom network (SAN) model. Inspired by the cluster structures, we further predicted an Au 4 two-dimensional (2D) monolayer and a three-dimensional (3D) crystal using graphene and diamond as templates, respectively. The computational results demonstrate that the two structures have high dynamic, thermal, and mechanical stabilities, and both structures exhibit metallic properties according to the band structures calculated at the HSE06 level. The chemical bonding analysis by the solid-state natural density partitioning (SSAdNDP) method indicates that they are superatomic crystals assembled by two electron Au 4 – superatoms. With this construction strategy, the new bonding pattern and properties of Au n L m are studied and the structure types of gold are enriched.

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Au₇₀S₂₀(PPh₃)₁₂ as Superatomic Analog to 18‐electron Transition‐Metal Complexes

Cited by 3 publications

References 77 publications

A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

Tri- and Tetra-superatomic Molecules in Ligand-Protected Face-Fused Icosahedral (M@Au₁₂)_n (M = Au, Pt, Ir, and Os, and n = 3 and 4) Clusters

Assembling Au₄ Tetrahedra to 2D and 3D Superatomic Crystals Based on Superatomic-Network Model

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Au70S20(PPh3)12 as Superatomic Analog to 18‐electron Transition‐Metal Complexes

Cited by 3 publications

References 77 publications

A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

Tri- and Tetra-superatomic Molecules in Ligand-Protected Face-Fused Icosahedral (M@Au12)n (M = Au, Pt, Ir, and Os, and n = 3 and 4) Clusters

Assembling Au4 Tetrahedra to 2D and 3D Superatomic Crystals Based on Superatomic-Network Model

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Au₇₀S₂₀(PPh₃)₁₂ as Superatomic Analog to 18‐electron Transition‐Metal Complexes

Tri- and Tetra-superatomic Molecules in Ligand-Protected Face-Fused Icosahedral (M@Au₁₂)_n (M = Au, Pt, Ir, and Os, and n = 3 and 4) Clusters

Assembling Au₄ Tetrahedra to 2D and 3D Superatomic Crystals Based on Superatomic-Network Model