Dopant-Dependent Electronic Structures Observed for M2Au36(SC6H13)24 Clusters (M = Pt, Pd)

Minseok Kim, Qing Tang, Alam Venugopal Narendra Kumar, Kyuju Kwak, Woojun Choi, De En Jiang, Dongil Lee

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43 Citations (Scopus)


Heteroatom doping is a powerful means to tune the optical and electronic properties of gold clusters at the atomic level. We herein report that doping a Au38 cluster with Pt and Pd atoms leads to core-doped [Pt2Au36(SC6H13)24]2- and [Pd2Au36(SC6H13)24]0, respectively. Voltammetric investigations show that these clusters exhibit drastically different electronic structures; whereas the HOMO-LUMO gap of [Pt2Au36(SC6H13)24]2- is found to be 0.95 V, that of [Pd2Au36(SC6H13)24]0 is drastically decreased to 0.26 V, suggesting Jahn-Teller distortion of the 12-electron cluster. Density functional investigations confirm that the HOMO-LUMO gap of the Pd-doped cluster is indeed reduced. Analysis of the optimized geometry for the 12-electron [Pd2Au36(SC6H13)24]0 reveals that the rod-like M2Au21 core becomes more flattened upon Pd-doping. Reversible geometrical interconversion between [Pt2Au36(SC6H13)24]0 and [Pt2Au36(SC6H13)24]2- is clearly demonstrated by manipulating the oxidation state of the cluster.

Original languageEnglish
Pages (from-to)982-989
Number of pages8
JournalJournal of Physical Chemistry Letters
Issue number5
Publication statusPublished - 2018 Mar 1

Bibliographical note

Funding Information:
D.L. acknowledges support by the Korea CCS R&D Center (KCRC) (Grant NRF-2014M1A8A1074219) and NRF Grants NRF-2017R1A2B3006651 and 2009-0093823. Computation by DFT was supported by the University of California, Riverside (Q.T.) and the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division (D.-e.J.).

Publisher Copyright:
© 2018 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Physical and Theoretical Chemistry


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