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Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties

Author

Listed:
  • Vivek Yadav

    (Indian Institute of Technology)

  • Arijit Jana

    (Indian Institute of Technology)

  • Swetashree Acharya

    (Indian Institute of Technology)

  • Sami Malola

    (University of Jyväskylä)

  • Harshita Nagar

    (Indian Institute of Technology)

  • Ankit Sharma

    (Indian Institute of Science Education and Research Bhopal)

  • Amoghavarsha Ramachandra Kini

    (Indian Institute of Technology)

  • Sudhadevi Antharjanam

    (Indian Institute of Technology)

  • Jan Machacek

    (The Czech Academy of Science)

  • Kumaran Nair Valsala Devi Adarsh

    (Indian Institute of Science Education and Research Bhopal)

  • Tomas Base

    (The Czech Academy of Science)

  • Hannu Häkkinen

    (University of Jyväskylä)

  • Thalappil Pradeep

    (Indian Institute of Technology)

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.

Suggested Citation

  • Vivek Yadav & Arijit Jana & Swetashree Acharya & Sami Malola & Harshita Nagar & Ankit Sharma & Amoghavarsha Ramachandra Kini & Sudhadevi Antharjanam & Jan Machacek & Kumaran Nair Valsala Devi Adarsh &, 2025. "Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties," Nature Communications, Nature, vol. 16(1), pages 1-13, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-56385-w
    DOI: 10.1038/s41467-025-56385-w
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    References listed on IDEAS

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    1. Chao Liu & Tao Li & Hadi Abroshan & Zhimin Li & Chen Zhang & Hyung J. Kim & Gao Li & Rongchao Jin, 2018. "Chiral Ag23 nanocluster with open shell electronic structure and helical face-centered cubic framework," Nature Communications, Nature, vol. 9(1), pages 1-6, December.
    2. Shang-Fu Yuan & Zong-Jie Guan & Wen-Di Liu & Quan-Ming Wang, 2019. "Solvent-triggered reversible interconversion of all-nitrogen-donor-protected silver nanoclusters and their responsive optical properties," Nature Communications, Nature, vol. 10(1), pages 1-7, December.
    3. Anil Desireddy & Brian E. Conn & Jingshu Guo & Bokwon Yoon & Robert N. Barnett & Bradley M. Monahan & Kristin Kirschbaum & Wendell P. Griffith & Robert L. Whetten & Uzi Landman & Terry P. Bigioni, 2013. "Ultrastable silver nanoparticles," Nature, Nature, vol. 501(7467), pages 399-402, September.
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