Size Evolution of the 2e-Superatom in Ligand-Protected Au Nanoclusters: Au2-(AuL)1-12 (L = CI, SH, SCH3, PH2, and P(CH3)2)

作者：Liu, Wangdan; Cheng, Longjiu^*

来源：Journal of Physical Chemistry C, 2016, 120(4): 2432-2438.

DOI：10.1021/acs.jpcc.5b10612

• GOLD CLUSTERS
• CRYSTAL-STRUCTURE
• STRUCTURAL EVOLUTION
• STRUCTURE PREDICTION
• IDENTIFICATION
• NANOPARTICLES
• AU-44(SR)(28)
• COMPLEXES
• OXIDATION
• NUCLEUS

Ligand-protected gold (Au-L) nanoclusters have attracted much attention due to their unique properties, and the superatom concept as a significantly well-known concept to explain the electronic stability was suggested. Although there has been a lot of major progress in this field, size evolution of the superatom is still little known because of limited experimental data. To give a direct and overall view of size evolution of the superatom in Au-L clusters, the Au-2-(AuL)(1-12) (L = Cl, SH, SCH3, PH2, P(CH3)(2)) system is taken as a test case. The global minimum geometries are studied by using a method combining the genetic algorithm with density functional theory. The gold cores in these structures consist of Au-3, Au-4, At-5, and Au-6 2e-superatoms protected by staple motifs. The 2e-superatoms were confirmed by chemical bonding analysis using the adaptive natural density partitioning method. The aromatic properties of the center of these compounds have been explored by the nucleus-independent chemical shift method, which indicates that the superatoms are highly aromatic. This work gives a clear size evolution of the 2e-superatomic Au-L clusters with 1 to 12 ligands, which discovers the growth mechanism of Au-L clusters with different ligands.

• 出版日期2016-2
• 单位安徽大学