Total Structure and Optical Properties of a Phosphine/Thiolate-Protected Au<sub>24</sub> Nanocluster

Das, Anindita; Li, Tao; Nobusada, Katsuyuki; Qiong, Zeng; Rosi, Nathaniel L.; Jin, Rongchao

doi:10.1021/ja3101566

Cited by 229 publications

(283 citation statements)

References 44 publications

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“…3 (36) Au22(dppo)6 (37) Au14(PPh3)8(NO3)4 (35) [Au24(PPh3)10(SC2H4Ph)5] + (38) [Au25(PPh3)10(SEt)5] 2+ (39) [Au39(PPh3)14Cl6] 2+ (40) appears to assist the holding of the cluster skeleton. [79]. The Au-Au bond distances in these icosahedron-based clusters (36)(37)(38)(39) are similar to those of smaller centered clusters, being in the range 2.63-3.23 Å ( Table 2).…”

Section: Higher-nuclearity Clustersmentioning

confidence: 58%

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Phosphine-Coordinated Pure-Gold Clusters: Diverse Geometrical Structures and Unique Optical Properties/Responses

Konishi

2014

Structure and Bonding

115

125

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Synthetic techniques, geometrical structures, and electronic absorption spectra of phosphine-coordinated pure-gold molecular clusters (PGCs) accumulated over 40 years are comprehensively collected especially for those with unambiguous X-ray crystal structures available. Inspection of the electronic absorption spectra from geometrical aspects reveals that their optical properties are highly dependent on the cluster geometries rather than the nuclearity. Recent examples of unusual clusters that show unique color / photoluminescence properties and their utilization for stimuli-responsive modules are also presented.

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Section: Higher-nuclearity Clustersmentioning

confidence: 58%

“…The spectra of higher-nuclearity centered clusters (36)(37)(38)(39) taken from the literatures [66,73,79,85] are summarized in Fig. 6b.…”

Section: Absmentioning

confidence: 99%

Phosphine-Coordinated Pure-Gold Clusters: Diverse Geometrical Structures and Unique Optical Properties/Responses

Konishi

2014

Structure and Bonding

115

125

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“…[25][26][27][28][29][30][31][32][33][34] A key challenge remaining for silver NCs is obtaining highly anisotropic shapes. In gold, NCs of anisotropic shapes were reported through solely thiols 35,36 and co-ligands of phosphines and thiols 37,38 . Such a strategy of co-ligands in sliver has failed to produce analogous results.…”

Section: Introductionmentioning

confidence: 99%

[Ag₆₇(SPhMe₂)₃₂(PPh₃)₈]³⁺: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster

Alhilaly¹,

Bootharaju²,

Joshi³

et al. 2016

J. Am. Chem. Soc.

174

134

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Engineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag67(SPhMe2)32(PPh3)8]3+. The crystal structure shows an Ag23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag23 core was formed through an unprecedented centered cuboctahedron, i.e., Ag13, unlike the common centered Ag13 icosahedron geometry. Two types of ligand motifs, eight AgS3P and eight bridging thiols, were found to stabilize the whole cluster. The optical spectrum of this NC displayed highly structured multiple absorption peaks. The electronic structure and optical spectrum of Ag67 were computed using time-dependent density functional theory (TDDFT) for both the full cluster [Ag67(SPhMe2)32(PPh3)8]3+ and a reduced model [Ag67(SH)32(PH3)8]3+. The lowest metal-to-metal transitions in the range 500–800 nm could be explained by considering the reduced model that shows almost identical electronic states to 32 free electrons in a jellium box. The successful synthesis of the large box-shaped Ag67 NC facilitated by the combined use of phosphine and thiol paves the way for synthesizing other metal clusters with unprecedented shapes by judicious choice of thiols and phosphines.

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“…Aikens, et.al studied the structural, electronic and optical properties of the thiolate-protected Au 38 (SR) 24 (R=CH 3 and C 6 H 13 ) cluster (40) and the origin of discrete optical absorption spectra of Au 25 (SH) 18 - 60 cluster with an icosahedral Au 114 core with 30 RS-Au-SR units as ligand and yielded an excellent fit of the structure factor to the experimental X-ray scattering structure factor (42). The optical absorption spectrum of Au 24 nanocluster protected by the mixed ligands of phosphine and thiolate was theoretically reproduced and interpreted (43). Most interestingly, ultrafast luminescence dynamics of thiolate protected Au 25 clusters indicated that their luminescence decay traces showed unique ultrafast growth and decay kinetics that are absent in the larger Au clusters (44).…”

Section: Introductionmentioning

confidence: 85%

Optical, Electrical, and Catalytic Properties of Metal Nanoclusters Investigated by ab initio Molecular Dynamics Simulation: A Mini Review

QG¹

2015

ACS Symposium Series

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Metal nanoclusters (e.g. Pt, Pd, and Au) have been those of the most valuable catalysts that have been used in many catalytic fields of hydrogenation, fuel-cell technologies, and water splitting photo-catalytically, etc. In this mini review, the previous works from our group about the optical, electrical and catalytic properties of metal nanoclusters, such as Pt 13 , Pd 13 , and Au 13 , have been reviewed. Ab initio molecular dynamics simulation (AIMD) at a DFT (Density Functional Theory) level has been applied to simulate the catalytic properties. The results show that Pt 13 and Pd 13 nanocluster present interesting hydrogen reduction and molecular H 2 desorption on the surface of the metal nanoclusters. An elementary hydrogen evolution mechanism on the metal nanocluster was established as H ads + +H ads + + 2e -+ M ads → [M ads -H ads -H ads ] → H 2 + M (M~metal). On the other hand, an Au nanocluster, which is protected by organic thiolate groups, was investigated by ab initio electron dynamics (AIED) calculation. The comparison between the protected and unprotected Au nanoclusters clarifies the contributions from Au core and organic thiolate ligands to the optical and electronic properties, such as photoexcitation, electron/hole relaxation, and energy dissipation, etc.

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Total Structure and Optical Properties of a Phosphine/Thiolate-Protected Au₂₄ Nanocluster

Cited by 229 publications

References 44 publications

Phosphine-Coordinated Pure-Gold Clusters: Diverse Geometrical Structures and Unique Optical Properties/Responses

Phosphine-Coordinated Pure-Gold Clusters: Diverse Geometrical Structures and Unique Optical Properties/Responses

[Ag₆₇(SPhMe₂)₃₂(PPh₃)₈]³⁺: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster

Optical, Electrical, and Catalytic Properties of Metal Nanoclusters Investigated by ab initio Molecular Dynamics Simulation: A Mini Review

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Total Structure and Optical Properties of a Phosphine/Thiolate-Protected Au24 Nanocluster

Cited by 229 publications

References 44 publications

Phosphine-Coordinated Pure-Gold Clusters: Diverse Geometrical Structures and Unique Optical Properties/Responses

Phosphine-Coordinated Pure-Gold Clusters: Diverse Geometrical Structures and Unique Optical Properties/Responses

[Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster

Optical, Electrical, and Catalytic Properties of Metal Nanoclusters Investigated by ab initio Molecular Dynamics Simulation: A Mini Review

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Product

Resources

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Total Structure and Optical Properties of a Phosphine/Thiolate-Protected Au₂₄ Nanocluster

[Ag₆₇(SPhMe₂)₃₂(PPh₃)₈]³⁺: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster