Competition of van der Waals and chemical forces on gold–sulfur surfaces and nanoparticles

Reimers, Jeffrey R.; Ford, Michael J.; Marcuccio, Sebastian M.; Ulstrup, Jens; Hush, Noel S.

doi:10.1038/s41570-017-0017

Cited by 117 publications

(139 citation statements)

References 161 publications

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“…Furthermore, not all the localized orbitals involved are purely metal orbitals, as the ligands have an important contribution. There is a significant amount of experimental and theoretical studies containing interactions with centers of gold and other heavy metal complexes and clusters reported in the literature . In this work, we will describe complexes depending on the type of interaction: intra‐ or intermolecular.…”

Section: Dispersion Interactions In Materials Based On Heavy Metalsmentioning

confidence: 99%

Noncovalent interactions in inorganic supramolecular chemistry based in heavy metals. Quantum chemistry point of view

Barrientos

Miranda-Rojas

Mendizábal

2018

Int J of Quantum Chemistry

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Complexity is a concept that is being considered in chemistry as it has shown potential to reveal interesting phenomena. Thus, it is possible to study chemical phenomena in a new approach called systems chemistry. The systems chemistry has an organization and function, which are regulated by the interactions among its components. At the simplest level, noncovalent interactions between molecules can lead to the emergence of large structures. Consequently, it is possible to go from the molecular to the supramolecular systems chemistry, which aims to develop chemical systems highly complex through intra-and intermolecular forces. Proper use of the interactions previously mentioned allow a glimpse of supramolecular system chemistry in many tasks such as structural properties reflecting certain behaviors in the chemistry of materials, for example, electrical and optical, processes of molecular recognition and among others. In the last time, within this area, inorganic supramolecular systems chemistry has been developed. Those systems have a structural orientation which is defined by certain forces that predominate in the associations among molecules. It is possible to recognize these forces as hydrogen bonding, π-π stacking, halogen bonding, electrostatic, hydrophobic, charge transfer, metal coordination, and metallophilic interactions. The presence of these forces in supramolecular system yields certain properties such as light absorption and luminescence. The quantum theoretical modeling plays an important role in the designing of the supramolecular system. The goal is to apply supramolecular principles in order to understand the associated forces in many inorganic molecules that include heavy metals for instance gold, platinum, and mercury. Relevant systems will be studied in detail, considering functional aspects such as enhanced coordination of functionalized molecular self-assembly, electronic and optoelectronic properties. K E Y W O R D Sdensity functional theory, dispersion term, Post-Hartree-Fock, van der Waals forces Grimme´s dispersion (D3)

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Section: Dispersion Interactions In Materials Based On Heavy Metalsmentioning

confidence: 99%

Noncovalent interactions in inorganic supramolecular chemistry based in heavy metals. Quantum chemistry point of view

Barrientos

Miranda-Rojas

Mendizábal

2018

Int J of Quantum Chemistry

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“…Based on the main mass (m/z) peak characteristics (see Figure S2, Supporting Information), the single Au(I)‐species were found to be the dominant species detected in the sample, though additional higher mass peaks were detectable which reflected the incomplete etching. Note that mass spectroscopic analyses of Au nanoclusters have been extensively reported . For the as‐etched samples, the presence of NCs with m / z peaks higher than single Au(I) species was as a result of the incomplete etching of the nanoparticles, which did not interfere with the STEM/TEM imaging analysis in this work, and thus the mass data were not further analyzed.…”

Section: Methodsmentioning

confidence: 98%

“…Metal nanoclusters (NCs) or nanoparticles (NPs) ranging from sub‐nanometer to nanometers have found increasing applications in catalysis, sensing, and medical diagnostics where the cluster or particle size and interparticle spatial characteristics play a key role in their functional properties. One important area of current research exploits the rich gold (Au)–thiolate (SR) chemistry for fabricating well‐defined NCs or NPs . For example, in a typical two‐phase synthesis of SR‐capped Au NPs or NCs under strong reducing conditions, Au(III) is first reduced to Au(I) by thiols, forming polymer‐like [Au(I)‐S(R)] n species, before further reducing to Au(0).…”

Section: Methodsmentioning

confidence: 99%

“…For example, in a typical two‐phase synthesis of SR‐capped Au NPs or NCs under strong reducing conditions, Au(III) is first reduced to Au(I) by thiols, forming polymer‐like [Au(I)‐S(R)] n species, before further reducing to Au(0). The NPs or NCs feature a shell layer of Au(I)‐SR staple motifs, rather than a pure SR monolayer, because thiols can reduce Au (III) to Au(I) and also oxidize Au(0) to Au(I) . The Au(I)‐SR motifs have found potential applications ranging from decorative finishes, ceramics, catalysis to medical care in areas such as rheumatoid arthritis, cancer, and Malaria .…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Nanoscale Lacing by Electrons

Cheng

Wang

et al. 2018

Small

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The ability to harness the optical or electrical properties of nanoscale particles depends on their assembly in terms of size and spatial characteristics which remains challenging due to lack of size focusing. Electrons provide a clean and focusing agent to initiate the assembly of nanoclusters or nanoparticles. Here an intriguing route is demonstrated to lace gold nanoclusters and nanoparticles in string assembly through electron-initiated nucleation and aggregative growth of Au(I)-thiolate motifs on a thin film substrate. This size-focused assembly is demonstrated by controlling the electron dose under transmission electron microscopic imaging conditions. The Au(I)-thiolate motifs, in combination with the molecularly mediated alignment, facilitate the interstring electrostatic and intrastring aurophilic interactions, which functions as a molecular template to aid electron-initiated 1D lacing. The findings demonstrate a hierarchical route for the 1D assemblies with size and spatial tunable catalytic, optical, sensing, and diagnostic properties.

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“…The bonds with the hot‐electron‐filled antibonding orbitals in the TNIs tend to cleave, resulting in desorption of adsorbed molecules or dissociated species. It is worth pointing out that coinage metal with fully occupied d bands can form strong chemical bonds with the soft Lewis base atoms, such as AuS bonds . The strong AuS bonding benefits the injection of hot electrons into the antibonding orbitals of the AuS bonds, leading to weaken the AuS bonds and eventually facilitate a cleavage of the AuS bonds.…”

Section: Injection Of Hot Electrons Into Surface Adsorbatesmentioning

confidence: 99%

Quantum‐Sized Metal Catalysts for Hot‐Electron‐Driven Chemical Transformation

Wei

Sun

2018

Advanced Materials

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Hot-electron-driven chemical transformation (HEDCT) represents an emerging research area in utilizing photoresponsive nanoparticles to enable efficient solar-to-chemical conversion. The unique properties of quantum-sized metal nanoparticles (QSMNPs) make them a class of photocatalysts that can generate hot electrons to drive surface chemical reactions with high quantum efficiency. Compared to the conventional thermal-driven chemical reactions, HEDCT offers the advantages of accelerating reaction rate, improving reaction selectivity, and possibly enabling the occurrence of thermodynamically endergonic reactions. Despite its embryonic stage of development, using QSMNPs for HEDCT shows great promise. Herein, a timely overview on the research progress is provided with a focus on the fundamental quantum processes involved in the photoexcitation of hot electrons and the following HEDCT on the surface of QSMNPs. The last section discusses the challenges, which also represent the opportunities for the materials research community, in designing robust QSMNP photocatalysts and understanding the fundamental quantum phenomena in HEDCT.

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Competition of van der Waals and chemical forces on gold–sulfur surfaces and nanoparticles

Cited by 117 publications

References 161 publications

Noncovalent interactions in inorganic supramolecular chemistry based in heavy metals. Quantum chemistry point of view

Noncovalent interactions in inorganic supramolecular chemistry based in heavy metals. Quantum chemistry point of view

Nanoscale Lacing by Electrons

Quantum‐Sized Metal Catalysts for Hot‐Electron‐Driven Chemical Transformation

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