Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties
Abstract We report the synthesis of [Ag17(o 1-CBT)12]3- abbreviated as Ag17, a stable 8e⁻ anionic cluster with a unique Ag@Ag12@Ag4 core-shell structure, where o 1-CBT is ortho-carborane-1-thiol. By substituting Ag atoms with Au and/or Cu at specific sites we created isostructural clusters [AuAg16(o...
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Nature Portfolio
2025-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-56385-w |
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| author | Vivek Yadav Arijit Jana Swetashree Acharya Sami Malola Harshita Nagar Ankit Sharma Amoghavarsha Ramachandra Kini Sudhadevi Antharjanam Jan Machacek Kumaran Nair Valsala Devi Adarsh Tomas Base Hannu Häkkinen Thalappil Pradeep |
| author_facet | Vivek Yadav Arijit Jana Swetashree Acharya Sami Malola Harshita Nagar Ankit Sharma Amoghavarsha Ramachandra Kini Sudhadevi Antharjanam Jan Machacek Kumaran Nair Valsala Devi Adarsh Tomas Base Hannu Häkkinen Thalappil Pradeep |
| author_sort | Vivek Yadav |
| collection | DOAJ |
| description | Abstract We report the synthesis of [Ag17(o 1-CBT)12]3- abbreviated as Ag17, a stable 8e⁻ anionic cluster with a unique Ag@Ag12@Ag4 core-shell structure, where o 1-CBT is ortho-carborane-1-thiol. By substituting Ag atoms with Au and/or Cu at specific sites we created isostructural clusters [AuAg16(o 1-CBT)12]3- (AuAg16), [Ag13Cu4(o 1-CBT)12]3- (Ag13Cu4) and [AuAg12Cu4(o 1-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. |
| format | Article |
| id | doaj-art-499f812a242c49119c0548d0cbd44e3a |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-499f812a242c49119c0548d0cbd44e3a2025-02-02T12:32:17ZengNature PortfolioNature Communications2041-17232025-01-0116111310.1038/s41467-025-56385-wSite-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic propertiesVivek Yadav0Arijit Jana1Swetashree Acharya2Sami Malola3Harshita Nagar4Ankit Sharma5Amoghavarsha Ramachandra Kini6Sudhadevi Antharjanam7Jan Machacek8Kumaran Nair Valsala Devi Adarsh9Tomas Base10Hannu Häkkinen11Thalappil Pradeep12DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence (TUE), Department of Chemistry, Indian Institute of TechnologyDST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence (TUE), Department of Chemistry, Indian Institute of TechnologyDST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence (TUE), Department of Chemistry, Indian Institute of TechnologyDepartment of Physics and Chemistry, Nanoscience Center, University of JyväskyläDST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence (TUE), Department of Chemistry, Indian Institute of TechnologyDepartment of Physics, Indian Institute of Science Education and Research BhopalDST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence (TUE), Department of Chemistry, Indian Institute of TechnologySophisticated Analytical Instruments Facility (SAIF), Indian Institute of TechnologyDepartment of Synthesis, Institute of Inorganic Chemistry, The Czech Academy of ScienceDepartment of Physics, Indian Institute of Science Education and Research BhopalDepartment of Synthesis, Institute of Inorganic Chemistry, The Czech Academy of ScienceDepartment of Physics and Chemistry, Nanoscience Center, University of JyväskyläDST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence (TUE), Department of Chemistry, Indian Institute of TechnologyAbstract We report the synthesis of [Ag17(o 1-CBT)12]3- abbreviated as Ag17, a stable 8e⁻ anionic cluster with a unique Ag@Ag12@Ag4 core-shell structure, where o 1-CBT is ortho-carborane-1-thiol. By substituting Ag atoms with Au and/or Cu at specific sites we created isostructural clusters [AuAg16(o 1-CBT)12]3- (AuAg16), [Ag13Cu4(o 1-CBT)12]3- (Ag13Cu4) and [AuAg12Cu4(o 1-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.https://doi.org/10.1038/s41467-025-56385-w |
| spellingShingle | Vivek Yadav Arijit Jana Swetashree Acharya Sami Malola Harshita Nagar Ankit Sharma Amoghavarsha Ramachandra Kini Sudhadevi Antharjanam Jan Machacek Kumaran Nair Valsala Devi Adarsh Tomas Base Hannu Häkkinen Thalappil Pradeep Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties Nature Communications |
| title | Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties |
| title_full | Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties |
| title_fullStr | Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties |
| title_full_unstemmed | Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties |
| title_short | Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties |
| title_sort | site specific substitution in atomically precise carboranethiol protected nanoclusters and concomitant changes in electronic properties |
| url | https://doi.org/10.1038/s41467-025-56385-w |
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