Double sigma-Aromaticity in a Planar Zinc-Doped Gold Cluster: Au9Zn-

Kulichenko, Maksim1; Chen, Wei-Jia2; Zhang, Yang-Yang3,4; Xu, Cong-Qiao5; Li, Jun3,4,5; Wang, Lai-Sheng2

2021-06-03

10.1021/acs.jpca.1c02954

JOURNAL OF PHYSICAL CHEMISTRY A   影响因子和分区

1089-5639

1520-5215

The strong relativistic effects result in many interesting chemical and physical properties for gold and gold compounds. One of the most surprising findings has been that small gold clusters prefer planar structures. Dopants can be used to tune the electronic and structural properties of gold nanoclusters. Here we report an experimental and theoretical investigation of a Zn-doped gold cluster, Au9Zn-. Photoelectron spectroscopy reveals that Au9Zn- is a highly stable electronic system with an electron binding energy of 4.27 eV. Quantum chemical studies show that the global minimum of Au9Zn- has a D-3h structure with a closed-shell electron configuration ((1)A(1)'), which can be viewed as replacing the central Au atom by Zn in the open-shell parent Au-10(-) cluster. The high electronic stability of Au9Zn- is corroborated by its extremely large HOMO-LUMO gap of 3.3 eV. Chemical bonding analyses revealed that the D-3h Au9Zn- are bonded by two sets of delocalized sigma bonds, giving rise to double sigma aromaticity and its remarkable stability. Two planar low-lying isomers are also observed, corresponding to a similar triangular structure with the Zn atom on the edge and another one with one of the corner Au atoms moved to the edge of the triangle.

SCI ; EI

英语

通讯

National Science Foundation[CHE-2053541] ; National Natural Science Foundation of China[22033005,22038002] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry ; Physics

Chemistry, Physical ; Physics, Atomic, Molecular & Chemical

WOS:000661116100012

AMER CHEMICAL SOC

CHEMISTRY

Web of Science

1.Utah State Univ, Dept Chem & Biochem, Logan, UT 84322 USA
2.Brown Univ, Dept Chem, Providence, RI 02912 USA
3.Tsinghua Univ, Dept Chem, Minist Educ, Beijing 100084, Peoples R China
4.Tsinghua Univ, Minist Educ, Key Lab Organ Optoelect & Mol Engn, Beijing 100084, Peoples R China
5.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China

Kulichenko, Maksim,Chen, Wei-Jia,Zhang, Yang-Yang,et al. Double sigma-Aromaticity in a Planar Zinc-Doped Gold Cluster: Au9Zn-[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2021,125(21).

Kulichenko, Maksim,Chen, Wei-Jia,Zhang, Yang-Yang,Xu, Cong-Qiao,Li, Jun,&Wang, Lai-Sheng.(2021).Double sigma-Aromaticity in a Planar Zinc-Doped Gold Cluster: Au9Zn-.JOURNAL OF PHYSICAL CHEMISTRY A,125(21).

Kulichenko, Maksim,et al."Double sigma-Aromaticity in a Planar Zinc-Doped Gold Cluster: Au9Zn-".JOURNAL OF PHYSICAL CHEMISTRY A 125.21(2021).