@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} } @article {139, title = {Self-Assembled p-Carborane Analog of p-Mercaptobenzoic Acid on Au{111}}, journal = {Chemistry of Materials}, volume = {27}, year = {2015}, month = {06/2015}, pages = {5425{\textendash}5435}, type = {Article}, chapter = {5425}, abstract = {

Thep-carborane cluster analog of p-mercaptobenzoic acid, 1

}, keywords = {boron compounds, carborane, crystallography, scanning tunneling microscopy, self-assembly}, doi = {10.1021/acs.chemmater.5b02263}, url = {http://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.5b02263}, author = {John C Thomas and Ishtvan Boldog and Harsharn S Auluck and Pablo J Bereciartua and Michal Dusek and Jan Machacek and Zdenek Bastl and Paul S Weiss and Tomas Base} } @proceedings {135, title = {Self-assembled monolayers of polyhedral dicarbadodecaborane dithiols: a computational assesment of high coverage patterns}, journal = {18th Interdisciplinary Surface Science Conference (ISSC-18)}, year = {2011}, publisher = {Institute of Physics, Organised by the IOP Thin Films and Surfaces Group}, address = {Warwick University, UK}, abstract = {

During the last decade, carborane thiols were introduced as building blocks for self-assembled monolayers on metal surfaces.[1, 2, 3] This work follows up the first calculations of dicarbadodecaborane dithiolate moieties on gold under sparse coverage.[4] Their results were used to place the polyhedral dithiolate moieties on a (111) gold surface as densely as possible, that is one moiety over six surface gold atoms, and compare computationally their various possible arrangements by DFT calculations of periodical systems using the Abinit program.[5] The
intermolecular interactions force the moieties to deviate from the bonding geometry found under sparse coverage, the two sulfur atoms are now positioned at almost equal height over the surface. The calculated stability of the monolayer formed by 9,12-dithiolate is again significantly higher than that of the layer build from 1,2-dithiolate moieties.

[1] T. Base, Z. Bastl, Z. Plzak, T. Grygar, J. Plesek, M. Carr, V. Malina, J. Subrt, J. Bohacek, E. Vecernikova, O. Kriz, Langmuir 21 (2005) 7776-7785.
[2] T. Base, Z. Bastl, V. Havr }, url = {http://www.iop.org/conferences}, author = {Jan Machacek} }