Structure-Activity Relationships of the Structural Analogs AuCu and AuAg in the Electrocatalytic CO Reduction Reaction.

Owing to the significant attention directed toward alloy metal nanoclusters, it is crucial to explore the relationship between their structures and their performance during the electrocatalytic CO reduction reaction (eCORR) and discover potential synergistic effects for the design of novel functional nanoclusters. However, a lack of suitable analogs makes this investigation challenging. In this study, we synthesized a well-defined pair of structural analogs, [AuCu(SAdm)(Dppm)Cl] and [AuAg(SAdm)(Dppm)Cl] (AuCu and AuAg, respectively), and characterized them.

Insights into the effect of regulation of molecular composition on the properties of (AuAg) clusters.

The precise tuning of cluster composition helps us to understand the relationship between clusters and their properties. In this context, on the basis of [AuAg(SAdm)(Dppm)](BPh) (HSAdm is 1-adamantanethiol, CHSH; Dppm is bis(diphenylphosphino)methane, PhPCHPPh), the control of the internal metal, surface thiol, and surface phosphine ligand was accomplished, with the formations of [AuAg(SAdm)(Dppm)](BPh), [AuAg(S-c-CH)(Dppm)](BPh) and [AuAg(SAdm)(VDPP-2H)](BPh) (HS-c-CH is cyclohexanethiol; VDPP is 1,1-bis(diphenylphosphino)ethylene, (PhP)CCH; and VDPP-2H is 1,1-bis(diphenylphosphine) ethane derived from the reduction of VDPP, (PhP)CHCH). The structures of [AuAg(SAdm)(Dppm)](BPh) and [AuAg(S-c-CH)(Dppm)](BPh) were determined by single-crystal X-ray crystallography (SC-XRD), while that of [AuAg(SAdm)(VDPP-2H)](BPh) was confirmed ESI-MS measurements.