Yadav Vivek, Jana Arijit, Acharya Swetashree, Malola Sami, Nagar Harshita, Sharma Ankit, Kini Amoghavarsha Ramachandra, Antharjanam Sudhadevi, Machacek Jan, Adarsh Kumaran Nair Valsala Devi, Base Tomas, Häkkinen Hannu, Pradeep Thalappil
DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence (TUE), Department of Chemistry, Indian Institute of Technology, Madras, Chennai, 600036, India.
Department of Physics and Chemistry, Nanoscience Center, University of Jyväskylä, FI 40014, Jyväskylä, Finland.
Nat Commun. 2025 Jan 30;16(1):1197. doi: 10.1038/s41467-025-56385-w.
We report the synthesis of [Ag(o-CBT)] abbreviated as Ag, a stable 8e⁻ anionic cluster with a unique Ag@Ag@Ag core-shell structure, where o-CBT is ortho-carborane-1-thiol. By substituting Ag atoms with Au and/or Cu at specific sites we created isostructural clusters [AuAg(o-CBT)] (AuAg), [AgCu(o-CBT)] (AgCu) and [AuAgCu(o-CBT)] (AuAgCu). These substitutions make systematic modulation of their structural and electronic properties. We show that Au preferentially occupies the core, while Cu localizes in the tetrahedral shell, influencing stability and structural diversity of the clusters. The band gap expands systematically (2.09 eV for Ag to 2.28 eV for AuAgCu), altering optical absorption and emission. Ultrafast optical measurements reveal longer excited-state lifetimes for Cu-containing clusters, highlighting the effect of heteroatom incorporation. These results demonstrate a tunable platform for designing nanoclusters with tailored electronic properties, with implications for optoelectronics and catalysis.
我们报道了[Ag(o-CBT)]（简称为Ag）的合成，它是一种稳定的8电子阴离子簇，具有独特的Ag@Ag@Ag核壳结构，其中o-CBT为邻碳硼烷-1-硫醇。通过在特定位置用Au和/或Cu取代Ag原子，我们制备了同构簇[AuAg(o-CBT)]（AuAg）、[AgCu(o-CBT)]（AgCu）和[AuAgCu(o-CBT)]（AuAgCu）。这些取代对它们的结构和电子性质进行了系统调节。我们发现Au优先占据核心，而Cu定位于四面体壳层，这影响了簇的稳定性和结构多样性。带隙系统地扩大（从Ag的2.09 eV到AuAgCu的2.28 eV），改变了光吸收和发射。超快光学测量揭示了含Cu簇的激发态寿命更长，突出了杂原子掺入的影响。这些结果展示了一个用于设计具有定制电子性质的纳米簇的可调平台，对光电子学和催化具有重要意义。
