Monolayer-Protected Cluster Molecules

Templeton, Allen C.; Wuelfing, and W. Peter; Murray, Royce W.

doi:10.1021/ar9602664

Cited by 2,375 publications

(2,316 citation statements)

References 53 publications

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“…19 Here the required threefold symmetry originates from TAPB, whereas the imine linkages to three again V-shaped ditopic TPDAL linkers result in a similar topology as for the examples above. This innovative approach yielded covalent STs, however, the formation of larger STs requires a specific conformation of the secondary TAPB(TPDAL) 3 building unit, and the frequent occurrence of deviating aggregates as e.g. homotactic nodes can disrupt the ST growth.…”

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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“…Figure 2a shows the DPV responses of C 6 Au MPCs in DCE with 0.05 M tetra-n-butylammonium perchlorate (TBAClO 4 ) as the supporting electrolyte. A series of well-resolved current peaks are spaced approximately the same distance apart on the potential axis.…”

Section: Resultsmentioning

confidence: 99%

“…15 Briefly, the prepared C 6 Au MPCs were first submitted to a ligand exchange reaction with 1,9-nonanedithiol. In a typical reaction, 60 mg of C 6 Au MPCs and 4 µL 1,9-nonanedithiol were co-dissolved in 10 mL of hexane in a round-bottom flask, and the mixture was stirred for about 36 h. During this period, some ligands on the particle surface were displaced by 1,9-nonanedithiol. Some precipitates were also found to stick on the flask wall due to the intercalation and cross-linking by the 1,9-nonanedithiol.…”

Section: Preparation Of Gold Slide Electrodesmentioning

confidence: 99%

Redox Properties of Self-Assembled Gold Nanoclusters

2005

J. Phys. Chem. B

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“…[3][4][5][6] At ambient temperature, both freely diffusing and electrode-attached MPCs demonstrate the voltammetric responses featuring a series of evenly spaced current peaks. 4,[7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] This ensemble behavior is equivalent to a series of classical Coulomb staircase charging events or sequential electrochemical redox reactions, which occur as MPCs encompass an intermediate dimension between small molecules and bulk materials.…”

Section: Introductionmentioning

confidence: 99%

Absolute Standard Redox Potential of Monolayer-Protected Gold Nanoclusters

2005

J. Phys. Chem. B

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The redox properties of monolayer-protected gold nanoclusters (MPCs) are considered from both the theoretical and experimental viewpoints. The "absolute standard redox potential" ([E Z/Z-1 0 ] abs ) of MPCs is first derived from electrostatic considerations. A linear dependence of the absolute standard redox potential on the valence state of MPCs is theoretically predicted and verified experimentally. By employing ferricinium/ferrocene (Fc + /Fc) as a reference redox couple, the average valence state of MPCs at a given potential can be estimated.

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Monolayer-Protected Cluster Molecules

Cited by 2,375 publications

References 53 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)

Redox Properties of Self-Assembled Gold Nanoclusters

Absolute Standard Redox Potential of Monolayer-Protected Gold Nanoclusters

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