Polymorphism in Self-Assembled Terphenylthiolate Monolayers on Au(111)

Bashir, Asif; Azzam, Waleed; Rohwerder, Michael; Terfort, Andreas

doi:10.1021/la403116r

Cited by 37 publications

(67 citation statements)

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“…From DFT calculations (not shown for the parallel configuration), the T‐shaped configuration is slightly more stable at the same TerPh coverage. We then opted for the latter configuration ( Figure a and details in the Supporting Information ) , in agreement with previous scanning tunneling microscopy observations on flat Au(111) surfaces …”

Section: Resultsmentioning

confidence: 75%

“…The DDT SAM was constructed according to a common model (Figure S7 and details in the Supporting Information). For arylthiols, different SAMs configurations are expected to be stable, depending on the experimental conditions: the parallel adsorption geometry via π−π interactions on unreconstructed gold or the paired adsorption via σ−π interactions on surface gold adatoms (“T‐shaped”). From DFT calculations (not shown for the parallel configuration), the T‐shaped configuration is slightly more stable at the same TerPh coverage.…”

Section: Resultsmentioning

confidence: 99%

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Quantified Binding Scale of Competing Ligands at the Surface of Gold Nanoparticles: The Role of Entropy and Intermolecular Forces

Goldmann

Ribot

Peiretti

et al. 2017

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A basic understanding of the driving forces for the formation of multiligand coronas or self-assembled monolayers over metal nanoparticles is mandatory to control and predict the properties of ligand-protected nanoparticles. Herein, H nuclear magnetic resonance experiments and advanced density functional theory (DFT) modeling are combined to highlight the key parameters defining the efficiency of ligand exchange on dispersed gold nanoparticles. The compositions of the surface and of the liquid reaction medium are quantitatively correlated for bifunctional gold nanoparticles protected by a range of competing thiols, including an alkylthiol, arylthiols of varying chain length, thiols functionalized by ethyleneglycol units, and amide groups. These partitions are used to build scales that quantify the ability of a ligand to exchange dodecanethiol. Such scales can be used to target a specific surface composition by choosing the right exchange conditions (ligand ratio, concentrations, and particle size). In the specific case of arylthiols, the exchange ability scale is exploited with the help of DFT modeling to unveil the roles of intermolecular forces and entropic effects in driving ligand exchange. It is finally suggested that similar considerations may apply to other ligands and to direct biligand synthesis.

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Section: Resultsmentioning

confidence: 75%

Section: Resultsmentioning

confidence: 99%

Quantified Binding Scale of Competing Ligands at the Surface of Gold Nanoparticles: The Role of Entropy and Intermolecular Forces

Goldmann

Ribot

Peiretti

et al. 2017

Small

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show abstract

“…5b). Typical distance between neighboring thiol-molecules in SAMs (e.g., dioctadecyl sulfide [40], terphenylthiolate [41] and azobenzene-thiol [42]) was reported to be around 5 Å. Therefore the recorded indistinct image was probably due to the overlap of electron cloud between neighboring molecules in monolayer as a result of the large lateral size of DAE group and a densely packed arrangement of thiol-based SAM.…”

Section: Lettersmentioning

confidence: 99%

Triazatriangulene platform for self-assembled monolayers of free-standing diarylethene

Wang

et al. 2018

Sci. China Mater.

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“…Structural order of aromatic thiol SAMs on Au(111) was considerably enhanced by increasing the number of phenyl ring in the molecular backbone [9][10][11] and by inserting the alkyl spacer between the phenyl ring and the sulfur atom.…”

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confidence: 99%

“…[6][7][8][9][10][11][12][13][14][15][16] However, there have been very few reports on the structure and orientation of SAMs of 4-alkylbenzenethiols with a nonpolar sustituent.…”

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confidence: 99%

Structural Investigation of 4-Methylbenzenethiol Self-Assembled Monolayers on Au(111) by Scanning Tunneling Microscopy

Kang¹,

Noh²

2014

Bulletin of the Korean Chemical Society

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Self-assembled Monolayers (SAMs) Formed by the Spontaneous Adsorption of Organic Thiols on Metal Surfaces offer a powerful route for potential applications in a variety of fields such as corrosion inhibition, lubrication, sensors, biointerface, and nanopatterning. [1][2][3][4] Recently, SAMs of aromatic thiols have drawn considerable attention due to their practical applications in molecular electronic devices. 5,6 It has been demonstrated that the work function of metal electrodes in electronic devices can be easily tuned by introducing the SAMs of ω-functionalized aromatic thiols with different functional group 5-8 and the performance of SAMmodified devices was strongly dependent on the molecular orientation of adsorbed molecules.8 Therefore, it is essential to understand the surface structure and molecular orientation of aromatic thiol SAMs as well as to control two-dimensional (2D) structure of SAMs for the development of electronic devices. Structural order of aromatic thiol SAMs on Au(111) was considerably enhanced by increasing the number of phenyl ring in the molecular backbone 9-11 and by inserting the alkyl spacer between the phenyl ring and the sulfur atom.12,13 High-resolution scanning tunneling microscopy (STM) imaging revealed that the adsorption of benzenethiol (BT) on Au(111) at 50°C led to the formation of well-ordered SAMs showing the (2 × 3√2)R30° structure, 9,12 while fluorinated benzenethiol SAMs have quite different packing strcutures.14,15 So far, numerous reports have mainly focused on the surface structure, molecular orientation, self-assembled process and physical property of SAMs formed by various aromatic thiols. 6-16 However, there have been very few reports on the structure and orientation of SAMs of 4-alkylbenzenethiols with a nonpolar sustituent. 17The main purpose of this work is to elucidate how much the alkyl substituent of benzenethiol at 4-position affects the formation and structure of SAMs. To explore this question, we examined 4-methylbenzenethiol (4-MBT) SAMs prepared in a 1 mM ethanol solution using STM, and revealed for the first time that 4-MBP molecules on Au(111) at 75 ºC form 2D ordered SAMs describing a (2√3 × √11.5)R30°s tructure.Atomically flat Au(111) substrates were prepared by thermal evaporation of gold onto mica as described previously.10 4-MBT SAMs were prepared by dipping the Au(111) substrate in a 1 mM ethanol solution of 4-MBT at room temperature or 75 °C for 2 h. STM measurements were carried out using a NanoScope E (Veeco, Santa Barbara, CA) with a commercial Pt/Ir (80:20) tip under ambient conditions. Imaging parameters were in the range of 300-500 mV for the bias voltage and in the range of 0.30-0.60 nA for the tunneling current between the tip and the sample.STM images in Figure 1 show the surface structures of 4-MBT SAMs on Au(111) formed after immersion in a 1 mM ethanol solution at room temperature and 75 °C for 2 h. The adsorption of 4-MBT molecules on Au(111) at room temperature yielded to the disordered SAMs containing gold adatom islands (bri...

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Polymorphism in Self-Assembled Terphenylthiolate Monolayers on Au(111)

Cited by 37 publications

References 62 publications

Quantified Binding Scale of Competing Ligands at the Surface of Gold Nanoparticles: The Role of Entropy and Intermolecular Forces

Quantified Binding Scale of Competing Ligands at the Surface of Gold Nanoparticles: The Role of Entropy and Intermolecular Forces

Triazatriangulene platform for self-assembled monolayers of free-standing diarylethene

Structural Investigation of 4-Methylbenzenethiol Self-Assembled Monolayers on Au(111) by Scanning Tunneling Microscopy

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