A New Binding Motif of Sterically Demanding Thiolates on a Gold Cluster

Nishigaki, Jun Ichi; Tsunoyama, Risako; Tsunoyama, Hironori; Ichikuni, Nobuyuki; Yamazoe, Seiji; Negishi, Yuichi; Ito, Misako; Matsuo, Tsukasa; Tamao, Kohei; Tsukuda, Tatsuya

doi:10.1021/ja305477a

Cited by 124 publications

(147 citation statements)

References 35 publications

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“…Reproduced with permission from Ref. [56]. of the smallest nanoalloys synthetically possible [60,61].…”

Section: Metal Dopants In Thiolate-protected Au Ncsmentioning

confidence: 99%

“…On the topic of Au-SR surface interactions, Au L 3 -edge EXAFS was employed by Tsukuda et al to investigate a unique binding motif for sterically demanding thiolates for Au 41 (S-Eind) 12 (S-Eind-1,1,3,3,5,5,7,7-octaethyl-s-hydrindacene-4-thiol) [56]. The total structure of Au 41 (S-Eind) 12 was not elucidated in this work or in previous work.…”

Section: Introduction To Gold Nanoclustersmentioning

confidence: 99%

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Bonding properties of thiolate-protected gold nanoclusters and structural analogs from X-ray absorption spectroscopy

Chevrier

Yang

Chatt

et al. 2015

Nanotechnology Reviews

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Abstract:Subnanometer, atomically precise thiolateprotected gold nanoclusters represent an important advancement in our understanding of thiolate-protected gold nanoparticles and thiolate-gold chemistry. Aside from being a link between larger gold nanoparticles and small gold complexes, gold nanoclusters exhibit extraordinary molecule-like optical, electronic, and physicochemical properties that are promising for next-generation imaging agents, sensing devices, or catalysts. The success in elucidating a number of unique thiolate-gold surface and gold core structures has greatly improved our understanding of thiolate-gold nanoclusters. Nevertheless, monitoring the structural and electronic behavior of thiolate-protected gold nanoclusters in a variety of media or environments is crucial for the next step in advancing this class of nanomaterials. Not to mention, there are a number of thiolateprotected gold nanoclusters with unknown structures or compositions that could reveal important insights on application-based properties such as luminescence or catalytic activity. This review summarizes some of the recent contributions from X-ray absorption spectroscopy (XAS) studies on the intriguing bonding properties of thiolate-protected gold nanoclusters and some structural analogs. Advantages from XAS include a local structural, site-and elementspecific analysis, suitable for ultra-small particle sizes (1-2 nm), along with versatile experimental conditions.

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“…Reproduced with permission from Ref. [56]. of the smallest nanoalloys synthetically possible [60,61].…”

Section: Metal Dopants In Thiolate-protected Au Ncsmentioning

confidence: 99%

Section: Introduction To Gold Nanoclustersmentioning

confidence: 99%

Bonding properties of thiolate-protected gold nanoclusters and structural analogs from X-ray absorption spectroscopy

Chevrier

Yang

Chatt

et al. 2015

Nanotechnology Reviews

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“…This occurs whenever steric interactions across the adatoms are too strong or steric intermolecular packing forces allow for very high surface coverages if both adatom and directly bound motifs coexist in the same regular SAM (15). The cross-adatom steric effect has also been demonstrated for gold nanoparticles (16), and we have shown that Coulombic interactions between charged tail groups can also inhibit adatom formation (17). SAMs involving adatoms have poor longrange order owing to the surface pitting that is required to deliver gold adatoms, while directly bound motifs lead to regular surfaces (18).…”

mentioning

confidence: 99%

Gold surfaces and nanoparticles are protected by Au(0)–thiyl species and are destroyed when Au(I)–thiolates form

Reimers

Ford

Halder

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

122

163

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The synthetic chemistry and spectroscopy of sulfur-protected gold surfaces and nanoparticles is analyzed, indicating that the electronic structure of the interface is Au(0)-thiyl, with Au(I)-thiolates identified as high-energy excited surface states. Density-functional theory indicates that it is the noble character of gold and nanoparticle surfaces that destabilizes Au(I)-thiolates. Bonding results from large van der Waals forces, influenced by covalent bonding induced through s-d hybridization and charge polarization effects that perturbatively mix in some Au(I)-thiolate character. A simple method for quantifying these contributions is presented, revealing that a driving force for nanoparticle growth is nobleization, minimizing Au(I)-thiolate involvement. Predictions that Brust-Schiffrin reactions involve thiolate anion intermediates are verified spectroscopically, establishing a key feature needed to understand nanoparticle growth. Mixing of preprepared Au(I) and thiolate reactants always produces Au(I)-thiolate thin films or compounds rather than monolayers. Smooth links to O, Se, Te, C, and N linker chemistry are established.gold-sulfur bonding | synthesis | mechanism | electronic structure | nanoparticle G old self-assembled monolayers (SAMs) and monolayerprotected gold nanoparticles form important classes of systems relevant for modern nanotechnological and sensing applications (1-5). Understanding the chemical nature of these interfaces is critical to the design of new synthesis techniques, the design of new spectroscopic methods to investigate them, and to developing system properties or device applications. Over the last 10 y, great progress has been made in understanding the atomic structures of gold-sulfur interfaces (6). Most discussion (7) has focused on the identification of adatom-bound motifs of the form RS-Au-SR (where R is typically a linear alkyl chain or phenyl group) sitting above a regular Au(111) surface (8-10) or on top of a nanoparticle core of regular geometry (11), Other variant structures have also been either observed, such as polymeric chains such as the trimer RS-Au-SR-Au-SR) (10, 11), or proposed (8,12,13). By considering the four isomers of butanethiol (14), we have shown that alternative structures can also be produced in which RS groups bind directly to an Au(111) surface without gold adatoms. This occurs whenever steric interactions across the adatoms are too strong or steric intermolecular packing forces allow for very high surface coverages if both adatom and directly bound motifs coexist in the same regular SAM (15). The cross-adatom steric effect has also been demonstrated for gold nanoparticles (16), and we have shown that Coulombic interactions between charged tail groups can also inhibit adatom formation (17). SAMs involving adatoms have poor longrange order owing to the surface pitting that is required to deliver gold adatoms, while directly bound motifs lead to regular surfaces (18).There is clearly a delicate balance between the forces that direct these different in...

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“…47,48 These bulky arenethiols and thiolates are useful ligands for transition metal complexes and clusters with unusual structures and oxidation states. Three related aspects are described here.…”

Section: Bulky Arenethiolsmentioning

confidence: 99%

“…47 The bulky (Eind)SH affords a cluster with the formula Au 41 [S(Eind)] 12 , which has an extremely low thiolate/Au ratio = 12/41, as well as an unusual number of Au atoms. …”

mentioning

confidence: 99%

Fused-Ring Bulky “Rind” Groups Producing New Possibilities in Elemento-Organic Chemistry

Matsuo

Tamao

2015

Bulletin of the Chemical Society of Japan

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Kinetic stabilization with sterically bulky substituents or ligands has played a pivotal role in exploring a large variety of unsaturated compounds or low-coordinated complexes. This article describes our findings that a series of fusedring octa-R-substituted s-hydrindacenyl groups (Rind groups), which we developed since 2007, can act as unique protecting groups both in main group chemistry and in transition-metal chemistry. The synthesis, structures, and properties of various types of highly reactive unsaturated and low-coordinated element-organic compounds of Groups 1, 2, 8, 11, and 1317 featuring the bulky Rind groups are covered.

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A New Binding Motif of Sterically Demanding Thiolates on a Gold Cluster

Cited by 124 publications

References 35 publications

Bonding properties of thiolate-protected gold nanoclusters and structural analogs from X-ray absorption spectroscopy

Bonding properties of thiolate-protected gold nanoclusters and structural analogs from X-ray absorption spectroscopy

Gold surfaces and nanoparticles are protected by Au(0)–thiyl species and are destroyed when Au(I)–thiolates form

Fused-Ring Bulky “Rind” Groups Producing New Possibilities in Elemento-Organic Chemistry

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