@article {167, title = {Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties}, journal = {Nature Communications}, volume = {16}, year = {2025}, month = {01/2025}, type = {Full article}, chapter = {1197}, abstract = {

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.

}, keywords = {Alloy, boron, carborane, Cluster, Copper, gold, luminescence, Metal, silver, Structure, thiol}, doi = {https://doi.org/10.1038/s41467-025-56385-w}, url = {https://www.nature.com/articles/s41467-025-56385-w}, author = {Vivek Yadav and Arijit Jana and Swetashree Acharya and Sami Malola and Harshita Nagar and Ankit Sharma and Amoghavarsha Ramachandra Kini and Sudhadevi Antharjanam and Jan Machacek and Kumaran Nair Valsala Devi Adarsh and Tomas Base and Hannu H{\"a}kkinen and Thalappil Pradeep} }