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

Research output: Contribution to journalArticle

18 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 languageEnglish
Pages (from-to)982-989
Number of pages8
JournalJournal of Physical Chemistry Letters
Volume9
Issue number5
DOIs
Publication statusPublished - 2018 Mar 1

Fingerprint

Electronic structure
Doping (additives)
electronic structure
Jahn-Teller effect
Electrons
Gold
Electronic properties
Optical properties
Atoms
Oxidation
Geometry
electrons
rods
gold
optical properties
oxidation
geometry
electronics
atoms

All Science Journal Classification (ASJC) codes

  • Materials Science(all)

Cite this

Kim, Minseok ; Tang, Qing ; Narendra Kumar, Alam Venugopal ; Kwak, Kyuju ; Choi, Woojun ; Jiang, De En ; Lee, Dongil. / Dopant-Dependent Electronic Structures Observed for M2Au36(SC6H13)24 Clusters (M = Pt, Pd). In: Journal of Physical Chemistry Letters. 2018 ; Vol. 9, No. 5. pp. 982-989.
@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",
year = "2018",
month = "3",
day = "1",
doi = "10.1021/acs.jpclett.7b03261",
language = "English",
volume = "9",
pages = "982--989",
journal = "Journal of Physical Chemistry Letters",
issn = "1948-7185",
publisher = "American Chemical Society",
number = "5",

}

Dopant-Dependent Electronic Structures Observed for M2Au36(SC6H13)24 Clusters (M = Pt, Pd). / Kim, Minseok; Tang, Qing; Narendra Kumar, Alam Venugopal; Kwak, Kyuju; Choi, Woojun; Jiang, De En; Lee, Dongil.

In: Journal of Physical Chemistry Letters, Vol. 9, No. 5, 01.03.2018, p. 982-989.

Research output: Contribution to journalArticle

TY - JOUR

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

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.

UR - http://www.scopus.com/inward/record.url?scp=85042696114&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85042696114&partnerID=8YFLogxK

U2 - 10.1021/acs.jpclett.7b03261

DO - 10.1021/acs.jpclett.7b03261

M3 - Article

AN - SCOPUS:85042696114

VL - 9

SP - 982

EP - 989

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

SN - 1948-7185

IS - 5

ER -