LAUSR

The precise tuning of cluster composition helps us to understand the relationship between clusters and their properties. In this context, on the basis of [Au4Ag5(SAdm)6(Dppm)2](BPh4) (HSAdm is 1-adamantanethiol, C10H15SH; Dppm is bis(diphenylphosphino)methane, Ph2PCH2PPh2), the control of the internal metal, surface thiol, and surface phosphine ligand was accomplished, with the formations of [Au6.5Ag2.5(SAdm)6(Dppm)2](BPh4), [Au4Ag5(S-c-C6H11)6(Dppm)2](BPh4) and [Au4Ag5(SAdm)6(VDPP-2H)2](BPh4) (HS-c-C6H11 is cyclohexanethiol; VDPP is 1,1-bis(diphenylphosphino)ethylene, (Ph2P)2CCH2; and VDPP-2H is 1,1-bis(diphenylphosphine) ethane derived from the reduction of VDPP, (Ph2P)2CHCH3). The structures of [Au6.5Ag2.5(SAdm)6(Dppm)2](BPh4) and [Au4Ag5(S-c-C6H11)6(Dppm)2](BPh4) were determined by single-crystal X-ray crystallography (SC-XRD), while that of [Au4Ag5(SAdm)6(VDPP-2H)2](BPh4) was confirmed via ESI-MS measurements. The control of the metal, thiol and phosphine ligand affects the electronic structure and optical properties of the [Au4Ag5(SAdm)6(Dppm)2](BPh4) cluster. Overall, the nanoclusters [Au4Ag5(SAdm)6(Dppm)2](BPh4), [Au6.5Ag2.5(SAdm)6(Dppm)2](BPh4), [Au4Ag5(S-c-C6H11)6(Dppm)2](BPh4) and [Au4Ag5(SAdm)6(VDPP-2H)2](BPh4) provide a chance to explore the effect of regulation of metals and surface ligands on electronic and optical properties.