Au16Cd16(SC6H11)20: A Glance at Structure‐Property Relationship

Doping Cd atom(s) into gold clusters is very promising in both theoretical study and practical applications. However, it has long been a challenge to synthesize heavily Cd‐doped AuCd bimetallic clusters and thereby reveal their structure‐property correlations. Herein a novel AuCd bimetallic cluster: Au16Cd16(SC6H11)20 (SC6H11 denotes deprotonated cyclohexanethiol) with a Cd to Au atomic ratio of 1:1 is reported. The precise structure of the cluster determined by single crystal X‐ray diffraction demonstrates that it has a unique hexatetrahedron Au14 core and a distinctive shell. Intriguingly, due to the special protecting motifs, the cluster exhibits high stability in various conditions studied, indicating that the geometric structure is crucial in determining the stability of the cluster. Most importantly, the photothermal property of the cluster has been investigated in comparison with those of M13‐kernel (M denotes metal atoms) clusters, and the results imply that the compactness and the Cd atom doping of the core play important roles in dictating the photothermal effect of the cluster. The authors believe that this work will provide some ideas for the rational design of clusters with high stability and excellent photothermal property. A novel AuCd cluster with the highest Cd‐Au ratio, Au16Cd16(SC6H11)20, is reported. It has a unique Au14 core and a distinctive shell comprised of Au‐Cd‐S synergistic protection motifs. The shell structure dictates the stability of the cluster, and most importantly, the core structure plays an essential role in tuning the photothermal properties of clusters.