Superatomic Ag_(58) nanoclusters incorporating a [MS_(4)@Ag_(12)]^(2+)(M = Mo or W) kernel show aggregation-induced emission

In core-shell silver nanoclusters,the control of core structure presents a more formidable challenge compared to that of the shell structure.Here,we report the successful synthesis and characterization of four distinct silver thiolate nanoclusters[MS_(4)@Ag_(12)@Ag_(46)S_(24)(dppb)_(12)](M=Mo or W),each incorporating a cup-like[MS_(4)@Ag_(12)]^(2+)kernel.These nanoclusters were meticulously prepared using(NH_(4))2Mo S4or(NH_(4))_(2)WS_(4)as both a template and a controlled source of S2-ions.Remarkably,we have observed a unique configuration within these eight-electron superatomic Ag_(58) nanoclusters,where the zerovalent Ag atoms reside exclusively within the inner[MS_(4)@Ag_(12)]^(2+)kernel.This stands in contrast to other superatomic clusters possessing an Ag(0)core.Notably,the introduction of phenyl-containing compounds during the synthesis process induced a transformation in the space group symmetry from C_(2)/c to I 4ˉ.This transformative effect was found to originate from the interplay between adjacent 1,4-bis(diphenylphosphino)butane(dppb)ligands,which facilitated enhanced emission through aggregationinduced intermolecular interactions,specifically C-H···πinteractions.Collectively,our findings contribute substantively to the understanding of the intricate relationship between nanocluster structures and their corresponding properties,shedding light on the crucial roles played by templates and diphosphine ligands in this context.

Structural diversification of tin-oxo complexes through controlled self-assembly and ligand modulation

Metal oxo clusters represent an intriguing class of compounds thatbridge the gap between single atoms and nanoparticles[1].These clusters possess atomically precise characteristics and offer unique advantages for unraveling the intricate relationships between structures andproperties[2–4].Among metal oxo clusters,tin dioxide(SnO_(2))stands outas a prominent n-type wide-bandgap semiconductor with numerous applications in gas sensors[5],extreme ultraviolet lithography[6],solarcells[7],and catalysts[8].Consequently,the synthesis of nanoclustermaterials based on SnO2 has attracted significant attention from thescientific community,driven by the pursuit of tailored properties.Acomprehensive understanding of the self-assembly processes governingtin-oxo clusters at the molecular level is crucial for designing syntheticroutes towards nanocluster materials with desired properties.