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Carboranethiol-Protected Propeller-Shaped Photoresponsive Silver Nanomolecule

  • Arijit Jana
    Arijit Jana
    Department of Science and Technology (DST) Unit of Nanoscience and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology (IIT) Madras, Chennai 600036, India
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  • Parvathy M. Unnikrishnan
    Parvathy M. Unnikrishnan
    Department of Science and Technology (DST) Unit of Nanoscience and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology (IIT) Madras, Chennai 600036, India
  • Ajay K. Poonia
    Ajay K. Poonia
    Department of Physics, Indian Institute of Science Education and Research Bhopal, Bhopal 462066, India
  • Jayoti Roy
    Jayoti Roy
    Department of Science and Technology (DST) Unit of Nanoscience and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology (IIT) Madras, Chennai 600036, India
    More by Jayoti Roy
  • Madhuri Jash
    Madhuri Jash
    Department of Science and Technology (DST) Unit of Nanoscience and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology (IIT) Madras, Chennai 600036, India
    More by Madhuri Jash
  • Ganesan Paramasivam
    Ganesan Paramasivam
    Department of Science and Technology (DST) Unit of Nanoscience and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology (IIT) Madras, Chennai 600036, India
  • Jan Machacek
    Jan Machacek
    Department of Synthesis, Institute of Inorganic Chemistry, The Czech Academy of Science 1001 Husinec, Rez 25068, Czech Republic
    More by Jan Machacek
  • Kumaran Nair Valsala Devi Adarsh*
    Kumaran Nair Valsala Devi Adarsh
    Department of Physics, Indian Institute of Science Education and Research Bhopal, Bhopal 462066, India
    *Email: [email protected]
  • Tomas Base*
    Tomas Base
    Department of Synthesis, Institute of Inorganic Chemistry, The Czech Academy of Science 1001 Husinec, Rez 25068, Czech Republic
    *Email: [email protected]
    More by Tomas Base
  • , and 
  • Thalappil Pradeep*
    Thalappil Pradeep
    Department of Science and Technology (DST) Unit of Nanoscience and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology (IIT) Madras, Chennai 600036, India
    *Email: pradeep.iitm.ac.in
Cite this: Inorg. Chem. 2022, 61, 23, 8593–8603
Publication Date (Web):May 27, 2022
https://doi.org/10.1021/acs.inorgchem.2c00186
Copyright © 2022 American Chemical Society
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Abstract

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We report the synthesis, structural characterization, and photophysical properties of a propeller-shaped Ag21 nanomolecule with six rotary arms, protected with m-carborane-9-thiol (MCT) and triphenylphosphine (TPP) ligands. Structural analysis reveals that the nanomolecule has an Ag13 central icosahedral core with six directly connected silver atoms and two more silver atoms connected through three Ag–S–Ag bridging motifs. While 12 MCT ligands protect the core through metal–thiolate bonds in a 3–6–3-layered fashion, two TPP ligands solely protect the two bridging silver atoms. Interestingly, the rotational orientation of a silver sulfide staple motif is opposite to the orientation of carborane ligands, resembling the existence of a bidirectional rotational orientation in the nanomolecule. Careful analysis reveals that the orientation of carborane ligands on the cluster’s surface resembles an assembly of double rotors. The zero circular dichroism signal indicates its achiral nature in solution. There are multiple absorption peaks in its UV–vis absorption spectrum, characteristic of a quantized electronic structure. The spectrum appears as a fingerprint for the cluster. High-resolution electrospray ionization mass spectrometry proves the structure and composition of the nanocluster in solution, and systematic fragmentation of the molecular ion starts with the loss of surface-bound ligands with increasing collision energy. Its multiple optical absorption features are in good agreement with the theoretically calculated spectrum. The cluster shows a narrow near-IR emission at 814 nm. The Ag21 nanomolecule is thermally stable at ambient conditions up to 100 °C. However, white-light illumination (lamp power = 120–160 W) shows photosensitivity, and this induces structural distortion, as confirmed by changes in the Raman and electronic absorption spectra. Femtosecond and nanosecond transient absorption studies reveal an exceptionally stable excited state having a lifetime of 3.26 ± 0.02 μs for the carriers, spread over a broad wavelength region of 520–650 nm. The formation of core-centered long-lived carriers in the excited state is responsible for the observed light-activated structural distortion.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c00186.

  • Experimental section, instrumentation, theoretical calculations, UV–vis, ESI-MS, CD, FESEM, EDS, PXRD, TEM, XPS, NMR, Fourier transform infrared, HOMO–LUMO, DSC, and associated figures (PDF)

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CCDC 2094436 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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Cited By

This article is cited by 3 publications.

  1. Arijit Jana, Wakeel Ahmed Dar, Sourav Kanti Jana, Ajay Kumar Poonia, Vivek Yadav, Jayoti Roy, Sourov Chandra, Kumaran Nair Valsala Devi Adarsh, Robin H. A. Ras, Thalappil Pradeep. Photoconversion of Ag31 to Ag42 Initiated by Solvated Electrons. Chemistry of Materials 2023, 35 (17) , 7020-7031. https://doi.org/10.1021/acs.chemmater.3c01293
  2. Arijit Jana, Madhuri Jash, Wakeel Ahmed Dar, Jayoti Roy, Papri Chakraborty, Ganesan Paramasivam, Sergei Lebedkin, Kaplan Kirakci, Sujan Manna, Sudhadevi Antharjanam, Jan Machacek, Monika Kucerakova, Sundargopal Ghosh, Kamil Lang, Manfred M. Kappes, Tomas Base, Thalappil Pradeep. Carborane-thiol protected copper nanoclusters: stimuli-responsive materials with tunable phosphorescence. Chemical Science 2023, 14 (6) , 1613-1626. https://doi.org/10.1039/D2SC06578A
  3. . Appendix. 2023, 601-637. https://doi.org/10.1016/B978-0-323-90879-5.00026-3

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