Three‐dimensional Octameric Assembly of Icosahedral M13 Units in [Au8Ag57(Dppp)4(C6H11S)32Cl2]Cl and its [Au8Ag55(Dppp)4(C6H11S)34][BPh4]2 Derivative

Abstract 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, [Au 8 Ag 57 (Dppp) 4 (C 6 H 11 S) 32 C l2 ]Cl (Dppp=1,3‐bis(diphenylphosphino)propane) showing a 3D octameric assembly mode involving the kernel penetration of eight complete icosahedral Au@Ag 10 Au 2 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 [Au 8 Ag 57 (Dppp) 4 (C 6 H 11 S) 32 Cl 2 ]Cl, with complete octameric fusion into [Au 8 Ag 55 (Dppp) 4 (C 6 H 11 S) 34 ][BPh 4 ] 2 , with incomplete octameric fusion. These observations will hopefully facilitate further research on the assembly of M 13 nanobuilding blocks.