Three-dimensional Octameric Assembly of Icosahedral M Units in [Au Ag (Dppp) (C H S) Cl ]Cl and its [Au Ag (Dppp) (C H S) ][BPh ] Derivative.

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 Ag (Dppp) (C H S) C ]Cl (Dppp=1,3-bis(diphenylphosphino)propane) showing a 3D octameric assembly mode involving the kernel penetration of eight complete icosahedral Au@Ag Au 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 Ag (Dppp) (C H S) Cl ]Cl, with complete octameric fusion into [Au Ag (Dppp) (C H S) ][BPh ] , with incomplete octameric fusion. These observations will hopefully facilitate further research on the assembly of M nanobuilding blocks.