Triple-Helical Self-Assembly of Atomically Precise Nanoclusters

Abstract

The construction of helical nanosized superstructures has long been a challenging pursuit, and little has been achieved in terms of atomic-level manipulation. Herein, intercluster hierarchical triple-helical structures were presented from all-thiol-stabilized Au6Cu6(4-MeOBT)12 nanoclusters by investigating their structures from both molecular and supramolecular aspects. Based on the atomically precise structure, the mechanism of intercluster assembly was elucidated, and the results indicated an intracluster rotation-induced self-assembly process. Specifically, the presence of abundant intermolecular interactions, including π–π stacking, C–H···O hydrogen bonding, and C–H···π interactions, was found to be beneficial for the organization of the triple-helical superstructure of metal clusters. Moreover, DFT calculations and UV–vis, Raman, and transient absorption measurements were performed to observe the different electronic structures between the nanocluster monomers and helical aggregates. Overall, this work presents an exciting example of the hierarchical triple-helical assembly of atomically precise nanoclusters, which allows an in-depth understanding of complex helical structures/behaviors at the atomic level.

Single‐Crystal Superstructures via Hierarchical Assemblies of Giant Rubik's Cubes as Tertiary Building Units

“…Then, such giant superclusters could further act as TBUs for assembling four single‐crystal superstructures. Unlike that the BUs were normally unisolable and at the same hierarchy level in previously reported superstructures, [7f, 9e, 11a] herein multi‐level BUs are isolable and can coexist in one single‐crystal structure. Thus, hierarchical assembly, as well as the evolution of superstructures from the one with coexisting isolable SBUs and TBUs to 3D assemblies of TBUs, is clearly demonstrated.…”

Probing the surface-active sites of metal nanoclusters with atomic precision: a case study of Au5Ag11

“…Indeed, both intramolecular and intermolecular interactions could restrict the vibration/rotation of cluster molecules and further improve their molecular properties. [57][58][59][60][61] The intermolecular interactions (such as C-H⋯F, C-H⋯π, π⋯π) were widely discovered in nanoclusters, while the study of the restriction of intramolecular rotations was insufficient in metal nanoclusters. In this work, we demonstrated that ligand engineering could be an efficient surface control strategy for activating the intra-/inter-molecular interactions of metal nanoclusters, achieving the functionalization of cluster-based nanomaterials.…”

Insights into the effect of regulation of molecular composition on the properties of (AuAg)9clusters

“…1–10 The monodisperse sizes, precise compositions, and accurate configurations of metal nanoclusters make them good templates for obtaining insights into the relationship between structures and properties at the atomic level, which in turn promotes the rational construction of new nanoclusters with customized performances. 11–18…”

“…[1][2][3][4][5][6][7][8][9][10] The monodisperse sizes, precise compositions, and accurate configurations of metal nanoclusters make them good templates for obtaining insights into the relationship between structures and properties at the atomic level, which in turn promotes the rational construction of new nanoclusters with customized performances. [11][12][13][14][15][16][17][18] For efficiently controlling the construction and compositions of nanoclusters at the atomic level to tune their properties, an alloying strategy for the manipulation of metal composition and a ligand-engineering strategy for the regu-lation of the surface structure have often been reported. [19][20][21][22][23][24] Asymmetrically doping a platinum atom into Au 38 can change its electron configuration and reactivity during electrocatalysis.…”