Bhat, Shridevi and Chakraborty, Indranath and Maark, Tuhina Adit and Mitra, Anuradha and De, Goutam and Pradeep, Thalappil (2016) Atomically precise and monolayer protected iridium clusters in solution. RSC Advances, 6 (32). pp. 26679-26688. ISSN 2046-2069

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The first atomically precise and monolayer protected iridium cluster in solution, Ir-9(PET)(6) (PET - 2-phenyethanethiol) was synthesized via a solid state method. The absence of a plasmonic band at similar to 350 nm, expected in the UV/Vis spectra for spherical Ir particles of 10 nm size indicated that the synthesized cluster is smaller than this dimension. Small angle X-ray scattering (SAXS) showed that the cluster has a particle size of similar to 2 nm in solution which was confirmed by transmission electron microscopy (TEM). The blue emission of the cluster is much weaker than many noble metal clusters investigated so far. X-ray photoelectron spectroscopy (XPS) measurements showed that all Ir atoms of the cluster are close to the zero oxidation state. The characteristic S-H vibrational peak of PET at 2560 cm(-1) was absent in the FT-IR spectrum of the cluster indicating RS-Ir bond formation. The molecular formula of the cluster, Ir-9(PET)(6) was assigned based on the most significant peak at m/z 2553 in the matrix assisted laser desorption ionization mass spectrum (MALDI MS), measured at the threshold laser intensity. Density functional theory calculations on small Ir@SCH3 and Ir@PET clusters and comparison of the predictions with the IR and H-1-NMR spectra of Ir-9(PET)(6) suggested that the PET ligands have two distinct structural arrangements and are likely to be present as bridging thiolates -(Ir-SR-Ir)-and singly attached thiolates -(Ir-SR).

Item Type: Article
Subjects: Engineering Materials
Divisions: Nano-Structured Materials
Depositing User: Bidhan Chaudhuri
Date Deposited: 28 Oct 2016 10:38
Last Modified: 05 Jan 2017 10:11

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