Three-dimensional Octameric Assembly of Icosahedral M-13 Units in [Au8Ag57(Dppp)(4)(C6H11S)(32)Cl-2]Cl and [Au8Ag55(Dppp)(4)(C6H11S)(34)][BPh4](2) Derivative

摘要

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, [Au8Ag57(Dppp)(4)(C6H11S)(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@Ag10Au2 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 [Au8Ag57(Dppp)(4)(C6H11S)(32)Cl-2]Cl, with complete octameric fusion into [Au8Ag55(Dppp)(4)(C6H11S)(34)][BPh4](2), with incomplete octameric fusion. These observations will hopefully facilitate further research on the assembly of M-13 nanobuilding blocks.