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

doi:10.1021/acs.jpclett.7b03261

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

43 Citations (Scopus)

Abstract

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 language	English
Pages (from-to)	982-989
Number of pages	8
Journal	Journal of Physical Chemistry Letters
Volume	9
Issue number	5
DOIs	https://doi.org/10.1021/acs.jpclett.7b03261
Publication status	Published - 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

Access to Document

10.1021/acs.jpclett.7b03261

Cite this

@article{faef6dcffb0640cb8feed3ffd844f29e,

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

abstract = "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.",

author = "Minseok Kim and Qing Tang and {Narendra Kumar}, {Alam Venugopal} and Kyuju Kwak and Woojun Choi and Jiang, {De En} and Dongil Lee",

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: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

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doi = "10.1021/acs.jpclett.7b03261",

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T1 - Dopant-Dependent Electronic Structures Observed for M2Au36(SC6H13)24 Clusters (M = Pt, Pd)

AU - Kim, Minseok

AU - Tang, Qing

AU - Narendra Kumar, Alam Venugopal

AU - Kwak, Kyuju

AU - Choi, Woojun

AU - Jiang, De En

AU - Lee, Dongil

N1 - 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.

PY - 2018/3/1

Y1 - 2018/3/1

N2 - 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.

AB - 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.

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