Exploring intermetallic synergy has allowed a series of alloy nanoparticles with prominent chemical–physical properties to be produced. However, precise alloying based on a maintained template has long been a challenging pursuit, and little has been achieved for manipulation at the atomic level. Here, a nanosystem based on M29(S-Adm)18(PPh3)4 (where S-Adm is the adamantane mercaptan and M is Ag/Cu/Au/Pt/Pd) has been established, which leads to the atomically precise operation on each site in this M29 template. Specifically, a library of 21 species of nanoclusters ranging from monometallic to tetrametallic constitutions has been successfully prepared step by step with in situ synthesis, target metal-exchange, and forced metal-exchange methods. More importantly, owing to the monodispersity of each nanocluster in this M29 library, the synergetic effects on the optical properties and stability have been mapped out. This nanocluster methodology not only provides fundamental principles to produce alloy nanoclusters with multimetallic compositions and monodispersed dopants but also provides an intriguing nanomodel that enables us to grasp the intermetallic synergy at the atomic level.

The capture of cations with nanoclusters is a flourishing area in the nanocluster science due to their effects on both molecular chemistry and supramolecular chemistry. The capture of Cs+ is most concerned in this field for its capability of controlling the synthesis and assembly of nanoclusters. However, the atomically precise interaction between Cs+ ions and nanoclusters remains mysterious. In this paper, we report the first X-ray crystal structure of a Cs+-captured nanocluster, formulated as Cs3Ag29(SSR)12(DMF) x (x = 5, 6; SSR, 1,3-benzene dithiol). The capture of Cs+ with Ag29(SSR)12(PPh3)4 peels the PPh3 ligands off from the nanocluster surface, giving rise to Cs3Ag29(SSR)12(DMF) x . The Cs+–cluster interactions not only alter the geometric structure of the Ag29(SSR)12 kernel but also assemble Ag29(SSR)12 clusters into one-dimensional, cluster-based lines. Remarkable differences have been observed by comparing the optical properties of the Cs3Ag29(SSR)12(DMF) x nanocluster in solutions or in crystallized films. Overall, this work is of great significance for revealing both the Cs+-induced intracluster transformation of nanocluster structures and the Cs+-induced intercluster self-assembly.

We found that the PL intensity of Ag series nanocluster could be controlled by the contraction/expansion of the free valence electrons.

Au 4 Cu 4 (SAdm) 5 (Dppm) 2 ]Br and [Au 4 Cu 5 (C 6 H 11 S) 6 (Dppm) 2 ](BPh 4 ) (SAdmH = 1-adamantane mercaptan, C 10 H 15 SH; C 6 H 11 SH = cyclohexyl mercaptan; Dppm = bis-(diphenylphosphino)methane, Ph 2 PCH 2 PPh 2 ), which was well characterized by single-crystal X-ray crystallography (SCXC) and monitored by time-dependent UV−vis absorption spectroscopy. Surprisingly, by etching with cyclohexyl mercaptan (C 6 H 12 S), [Au 4 Cu 4 (SAdm) 5 (Dppm) 2 ] + was converted to [Au 4 Cu 5 (C 6 H 11 S) 6 (Dppm) 2 ] + , accompanied by the transformation of Cu 4 (SAdm) 5 to Cu 5 (C 6 H 11 S) 6 . Besides, a reversible transformation reaction can be achieved via HSAdm etching with [Au 4 Cu 5 (C 6 H 11 S) 6 (Dppm) 2 ] + . These reversible Cu−S motif transformations via thiol ligand engineering between [Au 4 Cu 4 (SAdm) 5 (Dppm) 2 ] + and [Au 4 Cu 5 (C 6 H 11 S) 6 (Dppm) 2 ] + present a new desirable model to tailor the structure of Au−Cu alloy nanoclusters capped with Dppm and thiol ligands at the atomic level.