Superatomic Ag58 nanoclusters incorporating a [MS4@Ag12]2+ (M = Mo or W) kernel show aggregation-induced emission
Jun-Jie Fang, Zheng Liu, Yun-Peng Xie*, Xing Lu*
Chinese Chemical Letters
https://doi.org/10.1016/j.cclet.2023.109345
Abstract
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 [MS4@Ag12@Ag46S24(dppb)12] (M = Mo or W), each incorporating a cup-like [MS4@Ag12]2+ kernel. These nanoclusters were meticulously prepared using (NH4)2MoS4 or (NH4)2WS4 as both a template and a controlled source of S2− ions. Remarkably, we have observed a unique configuration within these eight-electron superatomic Ag58 nanoclusters, where the zero-valent Ag atoms reside exclusively within the inner [MS4@Ag12]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 C2/c to I-4. This transformative effect was found to originate from the interplay between adjacent 1,4-bis(diphenylphosphino)butane (dppb) ligands, which facilitated enhanced emission through aggregation-induced intermolecular interactions, specifically C−H···π interactions. 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.
