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Title: Doping Golden Buckyballs: Cu@Au16- and Cu@Au17- Cluster Anions

Abstract

The discovery of the unique catalytic effects of gold nanoparticles on oxide substrates has stimulated a flurry of research into the structures and properties of free gold nanoclusters, which may hold the key to elucidating the catalytic mechanisms of supported gold clusters. One of the most remarkable results has been the discovery of planar gold cluster anions (Aun_) of up to twelve gold atoms and the 2D to 3D transition for clusters with n larger than 12. Among larger gold clusters, Au20 has been found to be a perfect tetrahedron. A more recent study of the structures of Aun_ cluster anions in the medium size range (n=15–19) has shown that clusters with n=16–18 possess unprecedented empty cage structures. In particular, the Au16_ cluster anion has an interesting tetrahedral structure with an inner diameter of about 5.5 0 and can be compared to the fullerenes (buckyballs). Although Au32 was first suggested to be a “24- carat golden fullerene”, subsequent studies showed that the Au32_ ion is in fact a low-symmetry compact 3D structure. Other larger gold cage clusters have also been proposed computationally, but none has been observed or is expected to be the global minimum. The cage structures of themore » cluster anions Au16_ and Au17_ have recently been confirmed by electron diffraction and thus they are the first experimentally confirmed and the smallest possible gold cages. The large empty space inside these cage clusters immediately suggested that they can be doped with a foreign atom to produce a new class of endohedral gold cages analogous to endohedral fullerenes.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
908731
Report Number(s):
PNNL-SA-54881
Journal ID: ISSN 0570-0833; ACIEAY; 3423a; 25099; KP1704020; TRN: US200722%%764
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Angewandte Chemie International Edition, 46(16):2915-2918; Journal Volume: 46; Journal Issue: 16
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; COPPER; GOLD; MOLECULAR CLUSTERS; CRYSTAL STRUCTURE; ELECTRON DIFFRACTION; Environmental Molecular Sciences Laboratory

Citation Formats

Wang, Leiming, Bulusu, Satya, Zhai, Hua-jin, Zeng, Xiao Cheng, and Wang, Lai S. Doping Golden Buckyballs: Cu@Au16- and Cu@Au17- Cluster Anions. United States: N. p., 2007. Web. doi:10.1002/anie.200700060.
Wang, Leiming, Bulusu, Satya, Zhai, Hua-jin, Zeng, Xiao Cheng, & Wang, Lai S. Doping Golden Buckyballs: Cu@Au16- and Cu@Au17- Cluster Anions. United States. doi:10.1002/anie.200700060.
Wang, Leiming, Bulusu, Satya, Zhai, Hua-jin, Zeng, Xiao Cheng, and Wang, Lai S. Fri . "Doping Golden Buckyballs: Cu@Au16- and Cu@Au17- Cluster Anions". United States. doi:10.1002/anie.200700060.
@article{osti_908731,
title = {Doping Golden Buckyballs: Cu@Au16- and Cu@Au17- Cluster Anions},
author = {Wang, Leiming and Bulusu, Satya and Zhai, Hua-jin and Zeng, Xiao Cheng and Wang, Lai S.},
abstractNote = {The discovery of the unique catalytic effects of gold nanoparticles on oxide substrates has stimulated a flurry of research into the structures and properties of free gold nanoclusters, which may hold the key to elucidating the catalytic mechanisms of supported gold clusters. One of the most remarkable results has been the discovery of planar gold cluster anions (Aun_) of up to twelve gold atoms and the 2D to 3D transition for clusters with n larger than 12. Among larger gold clusters, Au20 has been found to be a perfect tetrahedron. A more recent study of the structures of Aun_ cluster anions in the medium size range (n=15–19) has shown that clusters with n=16–18 possess unprecedented empty cage structures. In particular, the Au16_ cluster anion has an interesting tetrahedral structure with an inner diameter of about 5.5 0 and can be compared to the fullerenes (buckyballs). Although Au32 was first suggested to be a “24- carat golden fullerene”, subsequent studies showed that the Au32_ ion is in fact a low-symmetry compact 3D structure. Other larger gold cage clusters have also been proposed computationally, but none has been observed or is expected to be the global minimum. The cage structures of the cluster anions Au16_ and Au17_ have recently been confirmed by electron diffraction and thus they are the first experimentally confirmed and the smallest possible gold cages. The large empty space inside these cage clusters immediately suggested that they can be doped with a foreign atom to produce a new class of endohedral gold cages analogous to endohedral fullerenes.},
doi = {10.1002/anie.200700060},
journal = {Angewandte Chemie International Edition, 46(16):2915-2918},
number = 16,
volume = 46,
place = {United States},
year = {Fri Apr 13 00:00:00 EDT 2007},
month = {Fri Apr 13 00:00:00 EDT 2007}
}
  • Structural, electronic, and magnetic properties of the golden cage doped with a transition-metal atom, MAu16(M=Fe,Co,Ni),are investigated using trapped ion electron diffraction, photoelectron spectroscopy, and density-functional theory. The best agreement to experiment is obtained for endohedral M@Au16 structures but with considerable distortions to the parent Au16 cage. Fe@Au16 and Co@Au16 are found to have similar structures with C2 symmetry while a C1 structure is obtained for Ni@Au16. The 4s electrons are observed to transfer to the Au16 cage, whereas atomiclike magnetism due to the unpaired 3d electrons is retained for all the doped clusters.
  • Structural, electronic, and magnetic properties of the golden cage doped with a transition-metal atom, M@Au 16¯ (M=Fe,Co,Ni), are investigated using trapped ion electron diffraction, photoelectron spectroscopy, and density-functional theory. The best agreement to experiment is obtained for endohedral M@Au 16¯structures but with considerable distortions to the parent Au 16¯ cage. Fe@Au 16¯ and Co@Au 16¯ are found to have similar structures with C 2 symmetry while a C 1 structure is obtained for Ni@Au 16¯. The 4s electrons are observed to transfer to the Au 16 cage, whereas atomiclike magnetism due to the unpaired 3d electrons is retained for allmore » the doped clusters.« less
  • In order to investigate the effect of polyoxometalate (POM) on the assembly of transition metal-bis(tetrazole) thioether complexes, three new complexes based on different Keggin anions and multinuclear Cu{sup I}-cluster [Cu{sup I}{sub 12}(bmtr){sub 9}(HSiMo{sub 12}O{sub 40}){sub 4}] (1), [Cu{sup I}{sub 3}(bmtr){sub 3}(PM{sub 12}O{sub 40})] (M=W for 2; Mo for 3) (bmtr=1,3-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)propane), have been hydrothermally synthesized and characterized by routine physical methods and single crystal X-ray diffraction. In compound 1, two kinds of nanometer-scale tetranuclear subunits linked by [SiMo{sub 12}O{sub 40}]{sup 4-} polyanions assemble a (3, 4)-connected three-dimensional (3D) self-penetrating framework. Compounds 2 and 3 are isostructural, exhibiting a 1D chain withmore » [PW{sub 12}O{sub 40}]{sup 3-}/[PMo{sub 12}O{sub 40}]{sup 3-} polyanions and trinuclear clusters arranging alternately. The distinct structural differences between these POM-based Cu{sup I}-bmtr complexes of 1 and 2/3 maybe rest on the contrast of Keggin-type polyoxometalate with different central heteroatoms, which have been discussed in detail. In addition, the electrochemical properties of the title complexes have been investigated. - Graphical abstract: Three new complexes based on different Keggin anions and multinuclear Cu{sup I}-cluster have been synthesized under hydrothermal conditions. The Keggin polyanions with different central heteroatoms play a key role. Highlights: Black-Right-Pointing-Pointer The flexible bis(tetrazole)-based thioether ligand with some advantages have been used. Black-Right-Pointing-Pointer The effect of Keggin anions with different central heteroatoms has been discussed in detail. Black-Right-Pointing-Pointer The electrochemical behaviors and electrocatalysis property have been investigated.« less
  • We have obtained the model exact static polarizability of the Cu{sub 4}O{sub 8} cluster within the three-band Hubbard model for different doping levels. The excitation gaps as well as the weight of the O{sup {minus}} (oxygen-hole) state in the ground-state wave function have been exactly computed. The parameters of the model are varied to alter the excitation gaps as well as the weight of the O{sup {minus}} state in order to examine the dependence of the polarizability on these quantities. The Cu{sub 4}O{sub 8} cluster is highly polarizable, the polarizability increasing with the doping level. The polarizability is large whenmore » the excitation gap is charge-transfer-like and increases with the decreasing gap; it also increases markedly with the increase in the weight of the O{sup {minus}} state. Experimentally, the {ital T}{sub {ital c}} in the cuprates is highest for the range of the weight of O{sup {minus}} for which the lattice is highly polarizable.« less
  • The discovery of catalytic effects in gold nanoparticles1 has accelerated efforts on the characterization and understanding of the structures and properties of bare gold clusters.2,3 Doped gold clusters have received increasing attention because of their potential tunable catalytic properties vs. dopant. The first highly stable doped gold cluster was a closed-shell icosahedral W@Au12, predicted using density-functional theory (DFT) by Pyykkö and Runeberg4 and confirmed using photoelectron spectroscopy (PES) by Li et al5. Subsequent PES studies showed that V-, Nb-, and Ta-doped Au12 clusters also possess the Ih symmetry.6 Mass spectra of a number of Au-alloy clusters have been observed bymore » Lievens and co-workers.« less