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, [Au8Ag57(Dppp)4(C6H11S)32Cl2]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)32Cl2]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 M13 nanobuilding blocks.

Electron counting and bonding patterns in assemblies of three and more silver-rich superatoms

“…A few larger superatom assemblies have been however characterized by Zhu and collaborators. 61,62 (Dppp = diphenylphosphinepropane) 62 appears much more intriguing. This 30-electron cluster possesses an Au 8 Ag 41 inner core of ideal D 2d symmetry that can be described as a cyclic assembly of eight interpenetrating Au@Ag 12 icosahedra (left side of Figure 11).…”

Chemical Flexibility of Atomically Precise Metal Clusters

“…Section dwells on the significance, emphasizing that the various coordination modes and coordination bonding energy play a very significant role in controlling the overall structure, stability, and reactivity of the cluster. ,, With regard to ligand inducements, incoming ligands can primarily displace existing ligands within the metal cluster by ligand-exchange reactions, which leads to forming new metal–ligand bonds and results in changes to the cluster’s structure and properties. ,,, Currently, there are two modes of ligand-induced cluster transformation chemistry: ligand exchange-induced structural transformations (LEIST) and postligand modifications inspired structural diversification. − Mainstream S-containing ligands exhibit stronger coordination ability, ,− while metal ions also display affinities toward ligands containing O/Se/Te, ,, P-based ligands, − N-containing ligands (N-hetero ring, and cyano-derivatives), − unsaturated C ligands (alkyne), , and halides (Cl, Br, and I). , The variations in the coordination ability of ligands are a dominant factor in chemical flexibility of metal clusters, which directly lead to the composition and structural changes in section of the critical interface layer (Scheme ). In certain instances, during ligand-exchange reactions of metal clusters, minor variations in groups of substituents at the terminals can cause either an increase or decrease in the number of metal atoms, or even a complete conversion of the metal structure into clusters. ,− The driving forces for incoming ligands only with substitute modification are primarily the alteration of steric effects and/or the donating-withdrawing effects of ligands (Scheme ).…”

“…In the same year, the Zhu group also reported a case of phenylacetylen-induced transformation of alloy NCs. The starting [Au 8 Ag 57 (Dppp) 4 (C 6 H 11 S) 32 Cl 2 ]Cl (30e) NC comprises a core-shell structure, wherein the Au 8 Ag 41 kernel contains eight 3D octamerically fused Au@Ag 10 Au 2 units capped by an Ag 16 (C 6 H 11 S) 20 (Dppp) 4 shell with 12 bare μ 3 -S and two Cl atoms . For each Au@Ag 10 Au 2 , the surface Au atoms serve as the center for the growth of another icosahedron.…”

“…LEIST from [Au 8 Ag 57 (Dppp) 4 (CHT) 32 Cl 2 ] + to [Au 8 Ag 55 (Dppp) 4 (CHT) 34 ] 2+ , the polyhedron (red or blue) represents the complete icosahedral Au@Ag 10 Au 2 units or incomplete Au@Ag 9 Au 2 units (gray, C; pink, P; yellow, S; sky blue and green, Ag; light orange, Au) …”

Size Growth of Au4Cu4: From Increased Nucleation to Surface Capping

“…The process of metal-ion-induced structural transition was analyzed by UV–vis spectroscopy and electrospray ionization (ESI) mass spectroscopy and DFT calculations. However, the complexity of the surface structure makes it very difficult to trace the conversion details, such as where the active site of the metal-ion-induced structural transition is located and what possible intermediates are formed in the process. − Therefore, suitable template clusters will help to resolve the details of active sites and intermediates, promoting the understanding of how metal ions attack the starting products and what intermediates are generated as transition states to form the final products. − …”