Several recent studies have attempted to impart [Au 25 (SR) 18 ] − with new properties by doping with foreign atoms. In this study, we studied the effect of copper doping on the electronic structure, geometric structure, and stability of [Au 25 (SR) 18 ] − with the aim of investigating the effect of foreign atom doping of [Au 25 (SR) 18 ] − . Cu n Au 25−n (SC 2 H 4 Ph) 18 was synthesized by reducing complexes formed by the reaction between metal salts (copper and gold salts) and PhC 2 H 4 SH with NaBH 4 . Mass analysis revealed that the products contained Cu n Au 25−n (SC 2 H 4 Ph) 18 (n = 1−5) in high purity. Experimental and theoretical analysis of the synthesized clusters revealed that copper doping alters the optical properties and redox potentials of the cluster, greatly distorts its geometric structure, and reduces the cluster stability in solution. These findings are expected to be useful for developing design guidelines for functionalizing [Au 25 (SR) 18 ] − through doping with foreign atoms.

A phenylethanethiolate-protected Pd(2)Au(36)(SC(2)H(4)Ph)(24) cluster, which is a two-Pd atom-doped cluster of the well studied magic gold cluster Au(38)(SC(2)H(4)Ph)(24), was synthesized in high purity and its stability was investigated. The results demonstrate that Pd(2)Au(36)(SC(2)H(4)Ph)(24) is more stable than Au(38)(SC(2)H(4)Ph)(24) against degradation in solution and core etching by thiols.

A series of highly stable Cu-doped gold clusters with up to 9 Cu atoms per cluster, Cu(n)Au(25-n)(SeC8H17)18, were synthesized using selenolate ligands. Spectroscopic analyses demonstrated that increasing levels of Cu doping in a cluster gradually decreased its HOMO-LUMO gap and consequently shifted its photoluminescence emission to longer wavelengths. These clusters were capable of exhibiting higher levels of Cu doping as compared to analogous clusters containing thiolate ligands.