Quasi‐Dual‐Packed‐Kerneled Au49(2,4‐DMBT)27 Nanoclusters and the Influence of Kernel Packing on the Electrochemical Gap

Although face‐centered cubic (fcc), body‐centered cubic (bcc), hexagonal close‐packed (hcp), and other structured gold nanoclusters have been reported, it was unclear whether gold nanoclusters with mix‐packed (fcc and non‐fcc) kernels exist, and the correlation between kernel packing and the properties of gold nanoclusters is unknown. A Au49(2,4‐DMBT)27 nanocluster with a shell electron count of 22 has now been been synthesized and structurally resolved by single‐crystal X‐ray crystallography, which revealed that Au49(2,4‐DMBT)27 contains a unique Au34 kernel consisting of one quasi‐fcc‐structured Au21 and one non‐fcc‐structured Au13 unit (where 2,4‐DMBTH=2,4‐dimethylbenzenethiol). Further experiments revealed that the kernel packing greatly influences the electrochemical gap (EG) and the fcc structure has a larger EG than the investigated non‐fcc structure. Gold in the shell: A gold nanocluster with a shell electron count of 22 was synthesized and structurally resolved by X‐ray crystallography. The nanocluster contains a unique Au34 kernel with one quasi face‐centered‐cubic structured Au21 and one non‐fcc structured Au13 unit. The kernel packing greatly influences the electrochemical gap (EG), and the quasi‐fcc structure has a larger EG than the investigated non‐fcc structure.