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 Au-49(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 Au-49(2,4-DMBT)(27) contains a unique Au-34 kernel consisting of one quasi-fcc-structured Au-21 and one non-fcc-structured Au-13 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.