Surface environment complication makes Ag₂₉ nanoclusters more robust and leads to their unique packing in the supracrystal lattice

Abstract

Silver nanoclusters have received unprecedented attention in the cluster science owing to their promising functionalities and intriguing physical/chemical properties. However, the essential instability significantly impedes their extensive applications. We herein...

Emergent properties in supercrystals of atomically precise nanoclusters and colloidal nanocrystals

“…105 Ligand-ligand interactions, such as electrostatic interactions, hydrogen bonding, and van der Waals interactions between the peripheral ligands greatly affect NCL and NCR assembly and dictate the final SC structure. 37,[106][107][108][109] This is well demonstrated in the case of Ag 44 or Au 12 Ag 32 NCLs. 110 When the protecting ligands are 3,4-difluorothiophenol (HSPhF 2 ) or 4-fluorothiophenol (HSPhF), the NCLs assemble into triclinic SCs.…”

Robust Enantiomeric Two-Dimensional Assembly of Atomically Precise Silver Clusters

“…Atomically precise metal clusters have been emerging as a promising class of materials bridging the gap between molecules and metal nanoparticles, which have attracted much attention due to their precise chemical compositions and intriguing physicochemical properties. − A number of strategies have been developed to control the structure, size, composition, and property of metal clusters; among those, the surface-capping ligand design plays a vital role in determining the structures and properties of metal clusters. , Also, such a surface-capping ligand induced strategy is an efficient approach for intercluster assemblies of clusters in crystal lattices. − In addition to modulating the core size, stability, and supramolecular assembly of metal clusters, the employed surface-protecting ligands will also render physical and chemical properties of metal clusters including molecular chirality, photoluminescence, solubility, and catalysis …”

“…7,8 Also, such a surface-capping ligand induced strategy is an efficient approach for intercluster assemblies of clusters in crystal lattices. 9−12 In addition to modulating the core size, 13 stability, 14 and supramolecular assembly 9 of metal clusters, the employed surface-protecting ligands will also render physical and chemical properties of metal clusters including molecular chirality, 15 photoluminescence, 16 solubility, 17 and catalysis. 18 To date, chiral metal clusters protected by surface ligands have been attracting considerable research attention given their potential applications in enantioselective catalysis, chiral separation/recognition, sensing, biomedicine, and nonlinear optics.…”

“…On the other hand, the stability of structurally well-defined Ag clusters is always a major concern especially in the case of using weak monothiolate ligands. 14,18 To solve this problem, an efficient strategy is to assemble discrete zero-dimensional (0D) metal clusters into a 1D cluster-based chain or 2D/3D frameworks. 46−56 Those assembled metal clusters could adopt advantages of enriched structural diversity and enhanced molecular robustness.…”

“…To date, chiral metal clusters protected by surface ligands have been attracting considerable research attention given their potential applications in enantioselective catalysis, chiral separation/recognition, sensing, biomedicine, and nonlinear optics. ,,− Among various chiral metal clusters, most of them have been focused on the construction of atomically precise gold clusters; ,− in contrast, the preparation of Ag clusters with well-defined structures are still in their early stage of research advancement. ,− Moreover, the origin of the chirality of these chiral Ag clusters can be mainly classified as three categories: (a) chirality induced by surface chiral ligands, − (b) postmodification of achiral Ag clusters using chiral ligands, ,− and (c) chiral metallic cores of the Ag clusters with achiral ligands. , However, the synthesis of chiral Ag clusters without a chiral metallic core using achiral ligands has yet to be reported. On the other hand, the stability of structurally well-defined Ag clusters is always a major concern especially in the case of using weak monothiolate ligands. , To solve this problem, an efficient strategy is to assemble discrete zero-dimensional (0D) metal clusters into a 1D cluster-based chain or 2D/3D frameworks. − Those assembled metal clusters could adopt advantages of enriched structural diversity and enhanced molecular robustness. For instance, Zhu and co-workers reported that the introduction of a SbF 6 – linker could render the assembled 3D superatom complex inorganic framework physical properties of larger channels, special circularly polarized luminescence behavior, and increased stability .…”