Gold-Adatom-Mediated Bonding in Self-Assembled Short-Chain Alkanethiolate Species on the Au(111) Surface

Maksymovych, Peter; Sorescu, Dan C.; Yates, John T.

doi:10.1103/physrevlett.97.146103

Cited by 440 publications

(655 citation statements)

References 26 publications

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“…Supporting Information) as similarly observed for alkanethiols on Au(111). 10 Two different types of chains can be distinguished: Type A chains (Figure 2b at least because they are particularly suitable for high resolution microscopy. Sierpi ski hexagons could be synthesized in solution from bis-terpyridine building blocks coordinatively bound to 36 Ru and 6 Fe centers and imaged by STM after subsequent deposition onto Au(111).…”

Section: Resultsmentioning

confidence: 99%

From Au–Thiolate Chains to Thioether Sierpiński Triangles: The Versatile Surface Chemistry of 1,3,5-Tris(4-mercaptophenyl)benzene on Au(111)

et al. 2016

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Self-assembly of 1,3,5-tris(4-mercaptophenyl)benzene (TMB) -a three-fold symmetric, thiol functionalized aromatic molecule -was studied on Au(111) with the aim to realize extended Authiolate linked molecular architectures. The focus lay on resolving thermally activated structural and chemical changes by a combination of microscopy and spectroscopy. Thereby Scanning Tunneling Microscopy provided submolecularly resolved structural information, while the chemical state of sulfur was assessed by X-ray Photoelectron Spectroscopy. Directly after room temperature deposition only less well ordered structures were observed. Mild annealing promoted the first structural transition into ordered molecular chains, partly organized in homochiral molecular braids. Further annealing led to self-similar Sierpi ski triangles, while annealing at even higher temperatures again resulted in mostly disordered structures. Both the irregular aggregates observed at room temperature and the chains were identified as metalorganic assemblies, whereby two out of the three intermolecular binding motifs are energetically equivalent according to Density Functional Theory simulations. The emergence of Sierpi ski triangles is driven by a chemical transformation, i.e. the conversion of coordinative Au-thiolate to covalent thioether linkages, and can be further understood by Monte Carlo simulations. The great structural variance of TMB on Au(111) can on one hand be explained by the energetic equivalence of two binding motifs. On the other hand, the unexpected chemical transition even enhances the structural variance and results in thiol-derived covalent molecular architectures.3 KEYWORDS surface chemistry, on-surface synthesis, thiolate, thioether, fractals, STM, XPS, DFT, Monte CarloThe notorious affinity of thiols to gold is beneficial for molecular nano-science. 1 Important examples include ligation of gold nanoparticles, 2, 3 two probe conductance measurements of single molecules, [4][5][6][7] and surface functionalization of Au(111) by Self-Assembled Monolayers (SAMs). 8,9 All of these applications rely on anchoring via strong Au-thiolate bonds. Even though thiolate SAMs are widespread, structural details of the anchor bond were discussed controversially for a long time. Yet, a consensus seems to be reached insofar as Au-thiolate complexes formed with gold adatoms play an important role. 10 The promising properties of RSAu-SR linkages, in particular their electric conductance and their ability to form spontaneously on Au(111) motivated the present study with the aim to utilize these linkages for extended molecular nanostructures. To this end 1,3,5-tris(4-mercaptophenyl)benzene (TMB) as a threefold functionalized and suitable model compound for network formation is studied on Au(111).Owing to both the extended triphenylbenzene backbone and the three-point anchoring via thiolate-surface bonds, planar adsorption is anticipated as an important prerequisite for extended networks. In contrast to SAMs, where the prevalent monothiols adopt upri...

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Section: Resultsmentioning

confidence: 99%

From Au–Thiolate Chains to Thioether Sierpiński Triangles: The Versatile Surface Chemistry of 1,3,5-Tris(4-mercaptophenyl)benzene on Au(111)

et al. 2016

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“…Low temperature STM imaging conducted at low coverages (only a few % of a monolayer) on the methylthiolate species [76] provides evidence for an Audithiolate moiety in which the Au adatom occupies a bridge site relative to the underlying Au(111) surface layer; the two S headgroup atoms are bonded to opposite sides of this adatom such that they occupy near-atop sites relative to the underlying Au surface atoms ( fig 5). Notice that within this structure the thiolate S atoms actually adopt a two-fold coordinated bridging geometry, bonding both to the Au adatom and the Au surface atom directly below.…”

Section: Reconstruction and Au Adatomsmentioning

confidence: 99%

The interface structure of n-alkylthiolate self-assembled monolayers on coinage metal surfaces

Woodruff

2008

Phys. Chem. Chem. Phys.

124

150

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The current state of understanding of the structure of the metal/thiolate interface of nalkylthiolate 'self-assembled monolayers' (SAMs) on Cu(111), Ag(111) and Au (111) is reviewed. On Cu(111) and Ag (111) there is now clear evidence that adsorbate-induced reconstruction of the outermost metal layer occurs to a less atomically-dense structure, with the S head-group atom bonded to four-fold and three-fold coordinated hollow sites, respectively, and that intermolecular interaction plays some role in the periodicity of the resulting SAMs. On the far more heavily-studied Au(111) surface, the detailed interface structure remains controversial, but there is growing evidence for the role of Au-adatomthiolate moieties in the layer ordering.

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“…A mixture of ligand motifs on the cluster surface, including -RS-Au-SR-and -RSAu-SR-Au-SR-motifs, were proposed for the first time. In fact, a novel gold-substrate sulfur-headgroup interfacial structure for the self-assembled monolayers on Au(111), named as ''staple motif'' was also recognized at the time, 84 which co-indicated the strong bonding interactions between gold and sulfur at the interface. These results called for new physical pictures to understand the interfacial structure of RS-AuNPs.…”

Section: Information Required For Predicting the Structure Of A Complmentioning

confidence: 99%

Investigating the structural evolution of thiolate protected gold clusters from first-principles

2012

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Unlike bulk materials, the physicochemical properties of nano-sized metal clusters can be strongly dependent on their atomic structure and size. Over the past two decades, major progress has been made in both the synthesis and characterization of a special class of ligated metal nanoclusters, namely, the thiolate-protected gold clusters with size less than 2 nm. Nevertheless, the determination of the precise atomic structure of thiolate-protected gold clusters is still a grand challenge to both experimentalists and theorists. The lack of atomic structures for many thiolate-protected gold clusters has hampered our in-depth understanding of their physicochemical properties and size-dependent structural evolution. Recent breakthroughs in the determination of the atomic structure of two clusters, [Au 25 (SCH 2 CH 2 Ph) 18 ] q (q ¼ À1, 0) and Au 102 (p-MBA) 44 , from X-ray crystallography have uncovered many new characteristics regarding the gold-sulfur bonding as well as the atomic packing structure in gold thiolate nanoclusters. Knowledge obtained from the atomic structures of both thiolate-protected gold clusters allows researchers to examine a more general ''inherent structure rule'' underlying this special class of ligated gold nanoclusters. That is, a highly stable thiolate-protected gold cluster can be viewed as a combination of a highly symmetric Au core and several protecting gold-thiolate ''staple motifs'', as illustrated by a general structural formula [Au]

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Gold-Adatom-Mediated Bonding in Self-Assembled Short-Chain Alkanethiolate Species on the Au(111) Surface

Cited by 440 publications

References 26 publications

From Au–Thiolate Chains to Thioether Sierpiński Triangles: The Versatile Surface Chemistry of 1,3,5-Tris(4-mercaptophenyl)benzene on Au(111)

From Au–Thiolate Chains to Thioether Sierpiński Triangles: The Versatile Surface Chemistry of 1,3,5-Tris(4-mercaptophenyl)benzene on Au(111)

The interface structure of n-alkylthiolate self-assembled monolayers on coinage metal surfaces

Investigating the structural evolution of thiolate protected gold clusters from first-principles

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