title: Structural evolution of atomically precise thiolated bimetallic [Au(12+n)Cu₃₂(SR)(30+n)]⁴⁻ (n = 0, 2, 4, 6) nanoclusters.
abstract: A series of all-thiol stabilized bimetallic Au-Cu nanoclusters, [Au(12+n)Cu32(SR)(30+n)](4-) (n = 0, 2, 4, 6 and SR = SPhCF3), are successfully synthesized and characterized by X-ray single-crystal analysis and density functional theory (DFT) calculations. Each cluster consists of a Keplerate two-shell Au12@Cu20 core protected by (6 - n) units of Cu2(SR)5 and n units of Cu2Au(SR)6 (n = 0, 2, 4, 6) motifs on its surface. The size and structural evolution of the clusters is atomically controlled by the Au precursors and countercations used in the syntheses. The clusters exhibit similar optical absorption properties that are not dependent on the number of surface Cu2Au(SR)6 units. Although DFT suggests an electronic structure with an 18-electron superatom shell closure, the clusters display different thermal stabilities. [Au(12+n)Cu32(SR)(30+n)](4-) clusters with n = 0 and 2 are more stable than those with n = 4 and 6. Moreover, an oxidation product of the clusters, [Au13Cu12(SR)20](4-), is structurally identified to gain insight into how the clusters are oxidized.
authors.affiliation: State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Huayan
authors.initials: H
authors.lastname: Yang
authors.forename: Yu
authors.initials: Y
authors.lastname: Wang
authors.forename: Juanzhu
authors.initials: J
authors.lastname: Yan
authors.forename: Xi
authors.initials: X
authors.lastname: Chen
authors.forename: Xin
authors.initials: X
authors.lastname: Zhang
authors.forename: Hannu
authors.initials: H
authors.lastname: Häkkinen
authors.forename: Nanfeng
authors.initials: N
authors.lastname: Zheng