Browse
Submit Data
Databases
API
Help

Dataset Information

33 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Triptycene-terminated thiolate and selenolate monolayers on Au(111).

ABSTRACT: To study the implications of highly space-demanding organic moieties on the properties of self-assembled monolayers (SAMs), triptycyl thiolates and selenolates with and without methylene spacers on Au(111) surfaces were comprehensively studied using ultra-high vacuum infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy and thermal desorption spectroscopy. Due to packing effects, the molecules in all monolayers are substantially tilted. In the presence of a methylene spacer the tilt is slightly less pronounced. The selenolate monolayers exhibit smaller defect densities and therefore are more densely packed than their thiolate analogues. The Se-Au binding energy in the investigated SAMs was found to be higher than the S-Au binding energy.

SUBMITTER: Liu J

PROVIDER: S-EPMC5405688 | biostudies-literature | 2017

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Triptycene-terminated thiolate and selenolate monolayers on Au(111).

Liu Jinxuan J Kind Martin M Schüpbach Björn B Käfer Daniel D Winkler Stefanie S Zhang Wenhua W Terfort Andreas A Wöll Christof C

Beilstein journal of nanotechnology 20170420

To study the implications of highly space-demanding organic moieties on the properties of self-assembled monolayers (SAMs), triptycyl thiolates and selenolates with and without methylene spacers on Au(111) surfaces were comprehensively studied using ultra-high vacuum infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy and thermal desorption spectroscopy. Due to packing effects, the molecules in all monolayers are s ...[more]

PMID: 28503400

Similar Datasets

Improving the Switching Capacity of Glyco-Self-Assembled Monolayers on Au(111).

Project description:Self-assembled monolayers (SAMs) decorated with photoisomerizable azobenzene glycosides are useful tools for investigating the effect of ligand orientation on carbohydrate recognition. However, photoswitching of SAMs between two specific states is characterized by a limited capacity. The goal of this study is the improvement of photoswitchable azobenzene glyco-SAMs. Different concepts, in particular self-dilution and rigid biaryl backbones, have been investigated. The required SH-functionalized azobenzene glycoconjugates were synthesized through a modular approach, and the respective glyco-SAMs were fabricated on Au(111). Their photoswitching properties have been extensively investigated by applying a powerful set of methods (IRRAS, XPS, and NEXAFS). Indeed, the combination of tailor-made biaryl-azobenzene glycosides and suitable diluent molecules led to photoswitchable glyco-SAMs with a significantly enhanced and unprecedented switching capacity.

| S-EPMC6973251 | biostudies-literature

Nanoscale Work Function Contrast Induced by Decanethiol Self-Assembled Monolayers on Au(111).

Project description:In this paper, we obtain maps of the spatial tunnel barrier variations in self-assembled monolayers of organosulfurs on Au(111). Maps down to the sub-nanometer scale are obtained by combining topographic scanning tunneling microscopy images with dI/dz spectroscopy. The square root of the tunnel barrier height is directly proportional to the local work function and the dI/dz signal. We use ratios of the tunnel barriers to study the work function contrast in various decanethiol phases: the lying-down striped β phase, the dense standing-up φ phase, and the oxidized decanesulfonate λ phase. We compare the induced work function variations too: the work function contrast induced by a lying-down striped phase in comparison to the modulation induced by the standing-up φ phase, as well as the oxidized λ phase. By performing these comparisons, we can account for the similarities and differences in the effects of the mechanisms acting on the surface and extract valuable insights into molecular binding to the substrate. The pillow effect, governing the lowering of the work function due to lying-down molecular tails in the striped low density phases, seems to have quite a similar contribution as the surface dipole effect emerging in the dense standing-up decanethiol phases. The dI/dz spectroscopy map of the nonoxidized β phase compared to the map of the oxidized λ phase indicates that the strong binding of molecules to the substrate is no longer present in the latter.

| S-EPMC7594278 | biostudies-literature

Tip-enhanced Raman spectroscopy for structural analysis of two-dimensional covalent monolayers synthesized on water and on Au (111).

Project description:A two-dimensional (2D) covalent monolayer based on [4 + 4] cycloaddition reactions between adjacent anthracene units was synthesized at an air/water interface. For structural analysis, tip-enhanced Raman spectroscopy (TERS) provides direct evidence for the covalent bonds formed between monomer molecules. For the first time, progress of the photopolymerization reaction was monitored by irradiation (λ = 385 nm) of the monomer monolayer for different times, based on averaged TER spectra extracted from maps. In addition, a 2D polymerization on a Au (111) substrate was realized, which opens up new possibilities for such chemical transformations. This work uses TERS as a minimally invasive tool to investigate how the reaction conditions affect polymerization conversion. We show that the high sensitivity and the high spatial resolution of TERS can be used to estimate the crystallinity of 2D covalent monolayers, which is a key question in polymer synthesis.

| S-EPMC6984395 | biostudies-literature

Oxidized Monolayers of Epitaxial Silicene on Ag(111).

Project description:The properties of epitaxial silicene monolayers on Ag(111) at various levels of oxidation are determined through complementary density functional theory calculations and soft X-ray spectroscopy experiments. Our calculations indicate that moderate levels of oxidation do not cause a significant bandgap opening in the epitaxial silicene monolayer, suggesting that oxygen functionalization is not a viable mechanism for bandgap tuning while the silicene monolayer remains on its metallic substrate. In addition, moderate oxidation is calculated to strongly distort the hexagonal Si lattice, causing it to cluster in regions of highest oxygen adatom concentration but retain its 2D sheet structure. However, our experiments reveal that beam-induced oxidation is consistent with the formation of islands of bulk-like SiO2. Complete exposure of the monolayer to ambient conditions results in a fully oxidized sample that closely resembles bulk SiO2, of which a significant portion is completely detached from the substrate.

| S-EPMC4776149 | biostudies-literature

An Electron-Rich Cyclic (Alkyl)(Amino)Carbene on Au(111), Ag(111), and Cu(111) Surfaces.

Project description:The structural properties and binding motif of a strongly ?-electron-donating N-heterocyclic carbene have been investigated on different transition-metal surfaces. The examined cyclic (alkyl)(amino)carbene (CAAC) was found to be mobile on surfaces, and molecular islands with short-range order could be found at high coverage. A combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations highlights how CAACs bind to the surface, which is of tremendous importance to gain an understanding of heterogeneous catalysts bearing CAACs as ligands.

| S-EPMC7496406 | biostudies-literature

Highly Biaxially Strained Silicene on Au(111).

Project description:Many of graphene's remarkable properties arise from its linear dispersion of the electronic states, forming a Dirac cone at the K points of the Brillouin zone. Silicene, the 2D allotrope of silicon, is also predicted to show a similar electronic band structure, with the addition of a tunable bandgap, induced by spin-orbit coupling. Because of these outstanding electronic properties, silicene is considered as a promising building block for next-generation electronic devices. Recently, it has been shown that silicene grown on Au(111) still possesses a Dirac cone, despite the interaction with the substrate. Here, to fully characterize the structure of this 2D material, we investigate the vibrational spectrum of a monolayer silicene grown on Au(111) by polarized Raman spectroscopy. To enable a detailed ex situ investigation, we passivated the silicene on Au(111) by encapsulating it under few layers hBN or graphene flakes. The observed spectrum is characterized by vibrational modes that are strongly red-shifted with respect to the ones expected for freestanding silicene. By comparing low-energy electron diffraction (LEED) patterns and Raman results with first-principles calculations, we show that the vibrational modes indicate a highly (>7%) biaxially strained silicene phase.

| S-EPMC8154839 | biostudies-literature

Dehydrohalogenation Condensation Reaction of Phenylhydrazine with Cl-Terminated Si(111) Surfaces.

Project description:Formation of stable organic-inorganic contacts with silicon often requires oxygen- and carbon-free interfaces. Some of the general approaches to create such interfaces rely on the formation of a Si-N bond. A reaction of dehydrohalogenation condensation of Cl-terminated Si(111) surface with phenylhydrazine is investigated as a means to introduce a simple function to the surface using a -NH-NH2 moiety as opposed to previously investigated approaches. The use of substituted hydrazine allows for the formation of a stable structure that is less strained compared to the previously investigated primary amines and leads to minimal surface oxidation. The process is confirmed by a combination of infrared studies, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry investigations. Density functional theory is utilized to yield a plausible surface reaction mechanism and provide a set of experimental observables to compare with these data.

| S-EPMC5096846 | biostudies-literature

Mesoporous gold nanospheres <i>via</i> thiolate-Au(i) intermediates.

Project description:Mesoporous gold (mesoAu) nanospheres support enhanced (electro)catalytic performance owing to their three-dimensional (3D) interior mesochannels that expose abundant active sites and facilitate electron/mass transfers. Although various porous Nanostructured Au has been fabricated by electrochemical reduction, alloying-dealloying and hard/soft templating methods, successful synthesis of mesoAu nanospheres with tailorable sizes and porosities remains a big challenge. Here we describe a novel surfactant-directed synthetic route to fabricate mesoAu nanospheres with 3D interconnected mesochannels by using the amphiphilic surfactant of C22H45N+(CH3)2-C3H6-SH (Cl-) (C22N-SH) as the mesopore directing agent. C22N-SH can not only self-reduce trivalent Au(iii)Cl4 - to monovalent Au(i), but also form polymeric C22N-S-Au(i) intermediates via covalent bonds. These C22N-S-Au(i) intermediates facilitate the self-assembly into spherical micelles and inhibit the mobility of Au precursors, enabling the crystallization nucleation and growth of the mesoAu nanospheres via in situ chemical reduction. The synthetic strategy can be further extended to tailor the sizes/porosities and surface optical properties of the mesoAu nanospheres. The mesoAu nanospheres exhibit remarkably enhanced mass/specific activity and improved stability in methanol electrooxidation, demonstrating far better performance than non-porous Au nanoparticles and previously reported Au nanocatalysts. The synthetic route differs markedly from other long-established soft-templating approaches, providing a new avenue to grow metal nanocrystals with desirable nanostructures and functions.

| S-EPMC6615434 | biostudies-literature

Ordering of Air-Oxidized Decanethiols on Au(111).

Project description:Self-assembled monolayers (SAMs) of alkanethiols on gold are a commonly used platform for nanotechnology owing to their ease of preparation and high surface coverage. Unfortunately, the gold-sulfur bond is oxidized at ambient conditions which alters the stability and structure of the monolayer. We show using scanning tunneling microscopy and X-ray photoelectron spectroscopy that decanethiolate molecules oxidize into decanesulfonates that organize into a hitherto unknown striped phase. Air-exposed SAMs oxidize, as can be determined by a shift of the S 2p peak and the appearance of O 1s photoelectrons as part of the decanethiol monolayer transforms into a lamellae-like decanesulfonate structure when exposed to air. The herringbone structure of the Au(111) surface is preserved, indicating that the interaction between the molecules and the surface is rather weak as these findings are substantiated by density functional theory calculations.

| S-EPMC5911804 | biostudies-literature

Thioetherification of Br-Mercaptobiphenyl Molecules on Au(111).

Project description:Thioether polymers are fundamental for a variety of applications. Their synthesis is, however, more challenging than that of other metal-catalyzed reactions due to the reported detachment of the S atom during thermal activation. In this study, it has been demonstrated unambiguously that thermal annealing results in the thioetherification of the 4-bromo-4-mercaptobiphenyl molecule (Br-MBP) adsorbed on the surface of Au(111). Through complementary techniques, such as scanning tunneling microscopy, spectroscopy, and first-principle calculations, we have identified four reaction steps, involving sulfhydryl or bromine molecular functional groups and leading to the formation of intermolecular C-S bonds. To form the thioether polymer and to overcome the competitive formation of C-C bonds, two reaction steps, the dehalogenation, and dissociation of the S-Au bond, must occur simultaneously. We detail the electronic properties of the phenyl-sulfur bond and the polymer as a function of the ligand length. This result suggests a wider perspective of this chemical synthesis.

| S-EPMC9951239 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data