We report the synthesis of [Ag17(o1-CBT)12]3- abbreviated as Ag17, a stable 8e⁻ anionic cluster with a unique Ag@Ag12@Ag4 core-shell structure, where o1-CBT is ortho-carborane-1-thiol. By substituting Ag atoms with Au and/or Cu at specific sites we created isostructural clusters [AuAg16(o1-CBT)12]3- (AuAg16), [Ag13Cu4(o1-CBT)12]3- (Ag13Cu4) and [AuAg12Cu4(o1-CBT)12]3- (AuAg12Cu4). 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 Ag17 to 2.28 eV for AuAg12Cu4), 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.

Department of Physics and Chemistry Nanoscience Center University of Jyväskylä FI 40014 Jyväskylä Finland

Department of Physics Indian Institute of Science Education and Research Bhopal Bhopal 462066 India

Department of Synthesis Institute of Inorganic Chemistry The Czech Academy of Science Rez 25068 Czech Republic

DST Unit of Nanoscience Department of Chemistry Indian Institute of Technology Madras Chennai 600036 India

Sophisticated Analytical Instruments Facility Indian Institute of Technology Madras Chennai 600036 India

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