Three-dimensional (3D) Octameric Assembly of Icosahedral M13 Units in [Au8Ag57(Dppp)4(C6H11S)32Cl2]Cl and Its Derivatives [Au8Ag55(Dppp)4(C6H11S)34](BPh4)2.

: The high-dimensional (that is, three-dimensional (3D)) assembly of nanomaterials is an effective means of improving their properties; however, achieving this assembly at the atomic level remains challenging. Herein, we obtained a novel nanocluster, [Au8 Ag57 (Dppp)4 (C6 H11 S)32 Cl2 ]Cl (Dppp=1,3-bis(diphenylphosphino)propane) showing a 3D octameric assembly mode involving the kernel penetration of eight complete icosahedral Au@Ag10 Au2 units for the first time. The atomically precise structure was determined by single-crystal X-ray diffraction, and further confirmed by thermogravimetric analysis, X-ray photoelectron spectroscopy, and electrospray ionization mass spectrometry measurements. Furthermore, ligand-induced transformation prompted the conversion of [Au8 Ag57 (Dppp)4 (C6 H11 S)32 Cl2 ]Cl, with complete octameric fusion into [Au8 Ag55 (Dppp)4 (C6 H11 S)34 ][BPh4 ]2 , with incomplete octameric fusion. These observations will hopefully facilitate further research on the assembly of M13 nanobuilding blocks.