Crystal Structures of Two New Gold-Copper Bimetallic Nanoclusters: CuxAu25-x(PPh3)10(PhC2H4S)5Cl22+ and Cu3Au34(PPh3)13(tBuPhCH2S)6S23

Sha Yang; Jinsong Chai; Tao Chen; Bo Rao; Yiting Pan; Haizhu Yu; Manzhou Zhu

doi:10.1021/acs.inorgchem.6b02016

Crystal Structures of Two New Gold-Copper Bimetallic Nanoclusters: Cu_xAu_25-x(PPh₃)₁₀(PhC₂H₄S)₅Cl₂²⁺ and Cu₃Au₃₄(PPh₃)₁₃(^tBuPhCH₂S)₆S₂³

Inorg Chem. 2017 Feb 20;56(4):1771-1774. doi: 10.1021/acs.inorgchem.6b02016. Epub 2017 Jan 31.

Authors

Sha Yang¹, Jinsong Chai¹, Tao Chen¹, Bo Rao¹, Yiting Pan¹, Haizhu Yu¹, Manzhou Zhu¹

Affiliation

¹ Department of Chemistry and Center for Atomic Engineering of Advanced Materials, Anhui University , Hefei, Anhui 230601, People's Republic of China.

PMID: 28140578
DOI: 10.1021/acs.inorgchem.6b02016

Abstract

Herein, we report the synthesis and atomic structures of the cluster-assembled Cu_xAu_25-x(PPh₃)₁₀(PhCH₂CH₂S)₅Cl₂²⁺ and Cu₃Au₃₄(PPh₃)₁₃(^tBuPhCH₂S)₆S₂³⁺ nanoclusters (NCs). The atomic structures of both NCs were precisely determined by single-crystal X-ray crystallography. The Cu_xAu_25-x(PPh₃)₁₀(PhC₂H₄S)₅Cl₂²⁺ NC was assembled by two icosahedral M₁₃ via a vertex-sharing mode. The Cu atom partially occupies the top and waist sites and is monocoordinated with chlorine or thiol ligands. Meanwhile, the Cu₃Au₃₄(PPh₃)₁₃(^tBuPhCH₂S)₆S₂³⁺ NC can be described as three 13-atom icosahedra sharing three vertexes in a cyclic fashion. The three Cu atoms all occupy the internal positions of the cluster core. What is more important is that all three Cu atoms in Cu₃Au₃₄ are monocoordinated by the bare S atoms. The absorption spectra of the as-synthesized bimetallic NCs reveal that the additional metal doping and different cluster assemblies affect the electronic structure of the monometallic NCs.