Kinetics of Place-Exchange Reactions of Thiols on Gold Nanoparticles

Montalti, Marco; Prodi, Luca; Zaccheroni, Nelsi; Baxter, Richard J.; Teobaldi, Gilberto; Zerbetto, Francesco

doi:10.1021/la034581s

Cited by 122 publications

(162 citation statements)

References 12 publications

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“…Examples of past applications include ͑i͒ the adsorption of alkanes and 1-alkenes on Au͑111͒, 17 where the adsorption energies of short chains, up to C 10 , were reproduced with an average error of less than 1 kcal mol −1 , and the unexpected transition to disorder that occurs for the deposition of alkyl chains between 18 and 26 carbon atoms was explained; ͑ii͒ the apparent symmetry breaking of the present macrocyle on the Au surface; 12 ͑iii͒ the substitution kinetics of thiols on self-assembled monolayers; 18 ͑iv͒ the existence of two surface reconstructions for C 60 adsorbed on Au͑110͒, 19 and the adsorption and dynamics of DNA bases on Au͑111͒ where the energies of adsorption were also within 1 kcal mol −1 from the experimental values. 20 The model does not require a priori definitions of bonds between the atoms of the molecules and those of the metal.…”

Section: Methodsmentioning

confidence: 98%

Experimental and theoretical study of the adsorption of fumaramide [2]rotaxane on Au(111) and Ag(111) surfaces

Mendoza

Whelan

Jalkanen

et al. 2005

The Journal of Chemical Physics

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Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Mendoza, S. M., Whelan, C. M., Jalkanen, J-P., Zerbetto, F., Gatti, F., Kay, E. R., ... Rudolf, P. (2005 Thin films of fumaramide ͓2͔rotaxane, a mechanically interlocked molecule composed of a macrocycle and a thread in a "bead and thread" configuration, were prepared by vapor deposition on both Ag͑111͒ and Au͑111͒ substrates. X-ray photoelectron spectroscopy ͑XPS͒ and high-resolution electron-energy-loss spectroscopy were used to characterize monolayer and bulklike multilayer films. XPS determination of the relative amounts of carbon, nitrogen, and oxygen indicates that the molecule adsorbs intact. On both metal surfaces, molecules in the first adsorbed layer show an additional component in the C 1s XPS line attributed to chemisorption via amide groups. Molecular-dynamics simulation indicates that the molecule orients two of its eight phenyl rings, one from the macrocycle and one from the thread, in a parallel bonding geometry with respect to the metal surfaces, leaving three amide groups very close to the substrate. In the case of fumaramide ͓2͔rotaxane adsorption on Au͑111͒, the presence of certain out-of-plane phenyl ring and Au-O vibrational modes points to such bonding and a preferential molecular orientation. The theoretical and experimental results imply that the three-dimensional intermolecular configuration permits chemisorption at low coverage to be driven by interactions between the three amide functions of fumaramide ͓2͔rotaxane and the Ag͑111͒ or Au͑111͒ surface.

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Section: Methodsmentioning

confidence: 98%

Experimental and theoretical study of the adsorption of fumaramide [2]rotaxane on Au(111) and Ag(111) surfaces

Mendoza

Whelan

Jalkanen

et al. 2005

The Journal of Chemical Physics

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“…By focusing on the initial rapid regime, several groups 46 , 51 have determined a first-order dependence of the rate on the concentration of NPs (e.g. the concentration of existing ligands) and a (non-ideal) first-order dependence on the concentration of the incoming ligands (in this case, co-Ferrocenyloctanethiol).…”

Section: Mechanism Of Place-exchangementioning

confidence: 99%

Divalent Metal Nanoparticles

DeVries

Brunnbauer

et al. 2007

Science

607

534

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Metal nanoparticles hold promise for many scientific and technological applications, such as chemical and biological sensors, vehicles for drug delivery, and subdiffraction limit waveguides. To fabricate such devices, a method to position particles in specific locations relative to each other is necessary. Nanoparticles tend to spontaneously aggregate into ordered two-and three-dimensional assemblies, but achieving onedimensional structures is less straightforward. Because of their symmetry, nanoparticles lack the ability to bond along specific directions. Thus, the technological potential of nanoparticles would be greatly enhanced by the introduction of a method to break the interaction symmetry of nanoparticles, thus inducing valency and directional interparticle interactions.When a nanoparticle is coated with a mixture of two different ligands, the ligands have been shown to phase-separate into ordered domains encircling or spiraling around the core. Topological constraints inherent in assembling two-dimensional vectors (e.g., ligands) onto a sphere (the core of the nanoparticle) dictate the necessary formation of two diametrically opposed defect points within the ligand shell. The molecules at these points are not optimally stabilized by intermolecular interactions and thus these sites are highly reactive. By functionalizing the polar singularities with a third type of molecule, we generate divalent nanoparticles with "chemical handles" that can be used to direct the assembly of the particles into chains. For example, taking inspiration from the wellknown interfacial polymerization synthesis of nylon, we place carboxylic acid terminated molecules at the polar defect points and join the newly bifunctional nanoparticles into chains by reacting them with 1,6-diaminohexane through an interfacial reaction.Furthermore, we perform a full kinetic and thermodynamic characterization of the molecularly defined polar defect points. We demonstrate that the rate of place-exchange at these points is significantly faster than it is elsewhere in the ligand shell. We also determine the equilibrium constant and standard free energy of the place-exchange reaction at the polar defect sites and demonstrate that the reaction is strongly affected by the molecular environment, i.e. the composition of the ligand shell.

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“…A full first-principles description would require huge and, therefore, computationally inaccessible super cells as well as dynamical approaches to geometry optimization (as discussed in Section 2, defects in SAMs, such as vacancies or ad-atoms, are very likely not static objects). Alternatively, MD approaches relying on (semi)empirical force fields [251][252][253][254] combined with quantum-mechanical calculations on selected motifs hold a certain promise to provide additional insight. [255] Such approaches would also be required to asses the role of dynamic disorder on, e.g., the work-function modification; there, as reported in Section 3.2, the orientation of the molecular dipole moment is of critical importance and, as the orientation of elongated molecules in an SAM is a rather ''soft'' degree of freedom, spatial and temporal fluctuations of the work function must therefore be expected.…”

Section: Impact Of Molecular Packing Densitymentioning

confidence: 99%

Modeling the Electronic Properties of π‐Conjugated Self‐Assembled Monolayers

2010

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The modification of electrode surfaces by depositing self-assembled monolayers (SAMs) provides the possibility for controlled adjustment of various key parameters in organic and molecular electronic devices. Most important among them are the work function of the electrode and the relative alignment of its Fermi level with the conducting states in the SAM itself and with those in a subsequently deposited organic semiconductor. For the efficient application of such interface modifications it is crucial to reach a proper understanding of the relation between the chemical structure of a molecule, its molecular electronic characteristics, and the properties of the SAM formed by such molecules. Over the past years, quantum-mechanical calculations have proven to be a valuable tool for reaching a fundamental understanding of the relevant structure-property relations. Here, we provide a review over the field and report on recent progress in the modeling of the interfacial electronic properties of pi-conjugated SAMs. In addition to the insight that can be gained from simple electrostatic considerations, we focus on the quantum-mechanical description of the roles played by substituents, molecular backbones, chemical anchoring groups, and the packing density of molecules on the surface. Furthermore, we explicitly address the energy-level alignment at the interface between a prototypical organic semiconductor and a SAM-covered metal electrode and describe an approach suitable for extending the metallic character of the substrate onto the monolayer.

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Kinetics of Place-Exchange Reactions of Thiols on Gold Nanoparticles

Cited by 122 publications

References 12 publications

Experimental and theoretical study of the adsorption of fumaramide [2]rotaxane on Au(111) and Ag(111) surfaces

Experimental and theoretical study of the adsorption of fumaramide [2]rotaxane on Au(111) and Ag(111) surfaces

Divalent Metal Nanoparticles

Modeling the Electronic Properties of π‐Conjugated Self‐Assembled Monolayers

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