Chirality and Electronic Structure of the Thiolate-Protected Au-38 Nanocluster

Olga Lopez-Acevedo; Hironori Tsunoyama; Tatsuya Tsukuda; Hannu Hakkinen; Christine M. Aikens

doi:10.1021/ja102934q

Chirality and Electronic Structure of the Thiolate-Protected Au-38 Nanocluster

Olga Lopez-Acevedo
, Hironori Tsunoyama
, Tatsuya Tsukuda
, Hannu Hakkinen
, Christine M. Aikens^*

^*Tämän työn vastaava kirjoittaja

Ei julkaistu Aalto-yliopiston affiliaatiolla

University of Jyväskylä
Hokkaido University
Kansas State University

Tutkimustuotos: Lehtiartikkeli › Article › Scientific › vertaisarvioitu

395 Viittaukset (Web of Science)

Abstrakti

Structural, electronic, and optical properties of the thiolate-protected Au-38(SR)(24) cluster are studied by density-functional theory computations (R = CH3 and R = C6H13) and by powder X-ray crystallography (R = C12H25). A low-energy structure which can be written as Au-23@(Au(SR)(2))(3)(Au-2(SR)(3))(6) having a bi-icosahedral core and a chiral arrangement of the protecting gold thiolate Au,,(SR), units yields an excellent match between the computed (for R = C6H13) and measured (for R = C12H25) powder X-ray diffraction function. We interpret in detail the electronic structure of the Au-23 core by using a particle-in-a-cylinder model. Although the alkane thiolate ligands are achiral, the chiral structure of the ligand layer yields strong circular dichroism (CD) in the excitations below 2.2 eV for Au-38(SCH3)(24). Our calculated CD spectrum is in quantitative agreement with the previously measured low-energy CD signal of glutathione-protected Au-38(SG)(24). Our study demonstrates a new mechanism for the strong chiral response of thiolate-protected gold clusters with achiral metal cores and ligands.

Alkuperäiskieli	Englanti
Sivut	8210-8218
Sivumäärä	9
Julkaisu	Journal of the American Chemical Society
Vuosikerta	132
Numero	23
DOI - pysyväislinkit	https://doi.org/10.1021/ja102934q
Tila	Julkaistu - 16 kesäk. 2010
OKM-julkaisutyyppi	A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Rahoitus

The authors thank Risako Tsunoyama for preparing the Au<INF>38</INF>(SC<INF>12</INF>F<INF>25</INF>)<INF>24</INF> sample used in this work and Jaakko Akola for discussions. The XRD measurements were performed at the beamline (BL44B2) of RI KEN Materials Science in SPring-8 with the approval of RIKEN (Proposal No. 20090055) with support by Dr. Kenichi Kato and Prof. Masaki Takata. C.M.A. thanks the Air Force Office of Scientific Research (AFOSR) and the Defense Advanced Research Projects Agency (DARPA) for financial support under Award FA9550-09-1-0451. H.H. thanks the Academy of Finland for financial support. The computational resources were provided by the CSC the Finnish IT Center for Science in Espoo, Finland.

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10.1021/ja102934q

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title = "Chirality and Electronic Structure of the Thiolate-Protected Au-38 Nanocluster",

abstract = "Structural, electronic, and optical properties of the thiolate-protected Au-38(SR)(24) cluster are studied by density-functional theory computations (R = CH3 and R = C6H13) and by powder X-ray crystallography (R = C12H25). A low-energy structure which can be written as Au-23@(Au(SR)(2))(3)(Au-2(SR)(3))(6) having a bi-icosahedral core and a chiral arrangement of the protecting gold thiolate Au,,(SR), units yields an excellent match between the computed (for R = C6H13) and measured (for R = C12H25) powder X-ray diffraction function. We interpret in detail the electronic structure of the Au-23 core by using a particle-in-a-cylinder model. Although the alkane thiolate ligands are achiral, the chiral structure of the ligand layer yields strong circular dichroism (CD) in the excitations below 2.2 eV for Au-38(SCH3)(24). Our calculated CD spectrum is in quantitative agreement with the previously measured low-energy CD signal of glutathione-protected Au-38(SG)(24). Our study demonstrates a new mechanism for the strong chiral response of thiolate-protected gold clusters with achiral metal cores and ligands.",

keywords = "NANOCRYSTAL GOLD MOLECULES, OPTICAL-ABSORPTION SPECTRA, DENSITY-FUNCTIONAL THEORY, SIMPLE METAL-CLUSTERS, CIRCULAR-DICHROISM, CATALYTIC-ACTIVITY, AEROBIC OXIDATION, CRYSTAL-STRUCTURE, SODIUM CLUSTERS, SHELL STRUCTURE",

author = "Olga Lopez-Acevedo and Hironori Tsunoyama and Tatsuya Tsukuda and Hannu Hakkinen and Aikens, \{Christine M.\}",

year = "2010",

month = jun,

day = "16",

doi = "10.1021/ja102934q",

language = "English",

volume = "132",

pages = "8210--8218",

journal = "Journal of the American Chemical Society",

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T1 - Chirality and Electronic Structure of the Thiolate-Protected Au-38 Nanocluster

AU - Lopez-Acevedo, Olga

AU - Tsunoyama, Hironori

AU - Tsukuda, Tatsuya

AU - Hakkinen, Hannu

AU - Aikens, Christine M.

PY - 2010/6/16

Y1 - 2010/6/16

N2 - Structural, electronic, and optical properties of the thiolate-protected Au-38(SR)(24) cluster are studied by density-functional theory computations (R = CH3 and R = C6H13) and by powder X-ray crystallography (R = C12H25). A low-energy structure which can be written as Au-23@(Au(SR)(2))(3)(Au-2(SR)(3))(6) having a bi-icosahedral core and a chiral arrangement of the protecting gold thiolate Au,,(SR), units yields an excellent match between the computed (for R = C6H13) and measured (for R = C12H25) powder X-ray diffraction function. We interpret in detail the electronic structure of the Au-23 core by using a particle-in-a-cylinder model. Although the alkane thiolate ligands are achiral, the chiral structure of the ligand layer yields strong circular dichroism (CD) in the excitations below 2.2 eV for Au-38(SCH3)(24). Our calculated CD spectrum is in quantitative agreement with the previously measured low-energy CD signal of glutathione-protected Au-38(SG)(24). Our study demonstrates a new mechanism for the strong chiral response of thiolate-protected gold clusters with achiral metal cores and ligands.

AB - Structural, electronic, and optical properties of the thiolate-protected Au-38(SR)(24) cluster are studied by density-functional theory computations (R = CH3 and R = C6H13) and by powder X-ray crystallography (R = C12H25). A low-energy structure which can be written as Au-23@(Au(SR)(2))(3)(Au-2(SR)(3))(6) having a bi-icosahedral core and a chiral arrangement of the protecting gold thiolate Au,,(SR), units yields an excellent match between the computed (for R = C6H13) and measured (for R = C12H25) powder X-ray diffraction function. We interpret in detail the electronic structure of the Au-23 core by using a particle-in-a-cylinder model. Although the alkane thiolate ligands are achiral, the chiral structure of the ligand layer yields strong circular dichroism (CD) in the excitations below 2.2 eV for Au-38(SCH3)(24). Our calculated CD spectrum is in quantitative agreement with the previously measured low-energy CD signal of glutathione-protected Au-38(SG)(24). Our study demonstrates a new mechanism for the strong chiral response of thiolate-protected gold clusters with achiral metal cores and ligands.

KW - NANOCRYSTAL GOLD MOLECULES

KW - OPTICAL-ABSORPTION SPECTRA

KW - DENSITY-FUNCTIONAL THEORY

KW - SIMPLE METAL-CLUSTERS

KW - CIRCULAR-DICHROISM

KW - CATALYTIC-ACTIVITY

KW - AEROBIC OXIDATION

KW - CRYSTAL-STRUCTURE

KW - SODIUM CLUSTERS

KW - SHELL STRUCTURE

U2 - 10.1021/ja102934q

DO - 10.1021/ja102934q

M3 - Article

SN - 0002-7863

VL - 132

SP - 8210

EP - 8218

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 23

ER -

Chirality and Electronic Structure of the Thiolate-Protected Au-38 Nanocluster

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