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Molecular isomerization has been well established in small-sized organic molecules, whereas bulk inorganic solids present the phase transformation. Studies of molecular isomerization and phase tran...

Herein, we report a methodology to prepare atomically precise, azide-functionalized nanoclusters based on ligand-induced rearrangement. Three surface-clickable nanoclusters, including a “waist”-cli...

Owing to their atomically precise structures, metal nanoclusters have always served as model molecular tools to dissect nanoparticle surface chemistry and to investigate structure–property correlat...

The capture of cations with nanoclusters is a flourishing area in the nanocluster science due to their effects on both molecular chemistry and supramolecular chemistry. The capture of Cs+ is most c...

The essential force of self-assembly in the nanocluster range is not intrinsically understood to date. In this work, the synergistic effect between metals was exploited to render the self-assembly from the icosahedral M13 (M = Pd, Au) nano-building-blocks. Single-crystal X-ray diffraction analysis revealed that the two Pd1Au12 icosahedrons were linked by five halogen linkages, and the assembled structure was determined to be Pd2Au23(PPh3)10Br7. The finding of Au–halogen linkages in the rod-like M25 nanoclusters has not been previously reported. Furthermore, the calculations on Hirshfeld charge analysis were performed, which implied that the reduced electronic repulsion (induced by the synergistic effect of Pd and Au metals) between two icosahedral units promoted the assembly. This study sheds light on the deep understanding of the essential force of self-assembly from icosahedral nano-building-blocks.

In this work, we report a new size conversion from [Au25(SePh)18]− to [Au23(SePh)16]− nanoclusters under the reductive condition (NaBH4). This novel transformation induced by only reductant has not been reported before in the field of gold nanocluster. The conversion process is studied via MALDI mass spectrometry, and UV–vis spectroscopy. These results demonstrate that the [Au23(SePh)16]− nanocluster is directly obtained by pulling out two units of “Au-SeR” from the [Au25(SePh)18]− nanocluster, which is similar to the “small molecular” reaction. In order to further understand this novel conversion, DFT calculations were performed, in which, with addition of two H– in the [Au25(SeH)18]− model, two Au atoms will depart from the structure of the [Au25(SeH)18]−, which is consistent with the experimental results. Furthermore, the as-prepared [Au23(SePh)16]− nanoclusters can be converted into [Au25(PET)18]− nanocluster (PET = SCH2CH2Ph) with excess PET under the reductive condition, which is quite remarkable du...

In this study, we successfully synthesized the rod-like [Au25(PPh3)10(SePh)5Cl2]q (q = +1 or +2) nanoclusters through kinetic control. The single crystal X-ray crystallography determined their formulas to be [Au25(PPh3)10(SePh)5Cl2](SbF6) and [Au25(PPh3)10(SePh)5Cl2](SbF6)(BPh4), respectively. Compared to the previously reported Au25 coprotected by phosphine and thiolate ligands (i.e., [Au25(PPh3)10(SR)5Cl2]2+), the two new rod-like Au25 nanoclusters show some interesting structural differences. Nonetheless, each of these three nanoclusters possesses two icosahedral Au13 units (sharing a vertex gold atom) and the bridging “Au–Se(S)–Au” motifs. The compositions of the two new nanoclusters were characterized with ESI-MS and TGA. The optical properties, electrochemistry, and magnetism were studied by EPR, NMR, and SQUID. All these results demonstrate that the valence character significantly affects the properties of the “non-superatom” Au25 nanoclusters, and the changes are different from the previously repo...