Quasi-Dual-Packed-Kerneled Au-49(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.Natural Science Foundation of China [21222301, 21528303, 21603234, 21373176, 21771186, 21171170, 21573212]; National Basic Research Program of China [2013CB934302]; Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology [2014FXCX002]; CAS/SAFEA International Partnership Program for Creative Research TeamsSCI(E)ARTICLE4112644-126485