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1.
J Am Chem Soc ; 141(44): 17713-17720, 2019 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-31617709

RESUMO

Various two-dimensional (2D) carbon allotropes with nonalternant topologies, such as pentaheptites and phagraphene, have been proposed. Predictions indicate that these metastable carbon polymorphs, which contain odd-numbered rings, possess unusual (opto)electronic properties. However, none of these materials has been achieved experimentally due to synthetic challenges. In this work, by using on-surface synthesis, nanoribbons of the nonalternant graphene allotropes, phagraphene and tetra-penta-hepta(TPH)-graphene, have been obtained by dehydrogenative C-C coupling of 2,6-polyazulene chains. These chains were formed in a preceding reaction step via on-surface Ullmann coupling of 2,6-dibromoazulene. Low-temperature scanning probe microscopies with CO-functionalized tips and density functional theory calculations have been used to elucidate their structural properties. The proposed synthesis of nonalternant carbon nanoribbons from the fusion of synthetic line-defects may pave the way for large-area preparation of novel 2D carbon allotropes.

2.
Phys Rev Lett ; 122(19): 196101, 2019 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-31144947

RESUMO

The chemical structure and orientation of molecules on surfaces can be visualized using low temperature atomic force microscopy with CO-functionalized tips. Conventionally, this is done in constant-height mode by measuring the frequency shift of the oscillating force sensor. However, this method is unsuitable for analyzing 3D objects. We are using the tunneling current to track the topography while simultaneously obtaining submolecular resolution from the frequency shift signal. Thereby, the conformation of 3D molecules and the adsorption sites on the atomic lattice can be reliably determined.

3.
J Am Chem Soc ; 141(18): 7399-7406, 2019 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-31016976

RESUMO

Controlling the regioselectivity of C-H activation in unimolecular reactions is of great significance for the rational synthesis of functional graphene nanostructures, which are called nanographenes. Here, we demonstrate that the adsorption of tetranaphthyl- p-terphenyl precursors on metal surfaces can completely change the cyclodehydrogenation route and lead to obtaining planar benzo-fused perihexacenes rather than double [7]helicenes during solution synthesis. The course of the on-surface planarization reactions is monitored using scanning probe microscopy, which unambiguously reveals the formation of dibenzoperihexacenes and the structures of reaction intermediates. The regioselective planarization can be attributed to the flattened adsorption geometries and the reduced flexibility of the precursors on the surfaces, in addition to the different mechanism of the on-surface cyclodehydrogenation from that of the solution counterpart. We have further achieved the on-surface synthesis of dibenzoperioctacene by employing a tetra-anthryl- p-terphenyl precursor. The energy gaps of the new nanographenes are measured to be approximately 2.1 eV (dibenzoperihexacene) and 1.3 eV (dibenzoperioctacene) on a Au(111) surface. Our findings shed new light on the regioselectivity in cyclodehydrogenation reactions, which will be important for exploring the synthesis of unprecedented nanographenes.

4.
ACS Nano ; 13(1): 324-336, 2019 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-30550265

RESUMO

Selectivity is a key parameter for building customized organic nanostructures via bottom-up approaches. Therefore, strategies are needed that allow connecting molecular entities at a specific stage of the assembly process in a chemoselective manner. Studying the mechanisms of such reactions is the key to apply these transformations for the buildup of organic nanostructures on surfaces. Especially, the knowledge about the precise adsorption geometry of intermediates at different stages during the reaction process and their interactions with surface atoms or adatoms is of fundamental importance, since often catalytic processes are involved. We show the selective dehalogenation of 4-bromo-3″-iodo- p-terphenyl on the Cu(111) surface using bond imaging atomic force microscopy with CO-functionalized tips. The deiodination and debromination reactions are triggered either by heating or by locally applying voltage pulses with the tip. We observed a strong hierarchical behavior of the dehalogenation with respect to temperature and voltage. In connection with first-principles simulations we can determine the orientation and position of the pristine molecules as well as adsorbed mono/diradicals and the halogens. We find that the isolated radicals are chemisorbed to Cu(111) top sites, which are lifted by 16 pm ( meta-position) and 32 pm ( para-position) from the Cu surface plane. This leads to a strongly twisted and bent 3D adsorption structure. After heating, different types of dimers are observed whose molecules are either bound to surface atoms or connected via Cu adatoms. Such knowledge about the intermediate geometry and its interaction with the surface will open the way to rationally design syntheses on surfaces.

5.
Nat Commun ; 9(1): 3277, 2018 08 16.
Artigo em Inglês | MEDLINE | ID: mdl-30115915

RESUMO

Site-selective functionalization of only one of two identical chemical groups within one molecule is highly challenging, which hinders the production of complex organic macromolecules. Here we demonstrate that adsorption of 4,4″-diamino-p-terphenyl on a metal surface leads to a dissymmetric binding affinity. With low temperature atomic force microscopy, using CO-tip functionalization, we reveal the asymmetric adsorption geometries of 4,4″-diamino-p-terphenyl on Cu(111), while on Au(111) the symmetry is retained. This symmetry breaking on Cu(111) is caused by a lattice mismatch and interactions with the subsurface atomic layer. The dissymmetry results in a change of the binding affinity of one of the amine groups, leading to a non-stationary behavior under the influence of the scanning tip. Finally, we exploit this dissymmetric binding affinity for on-surface self-assembly with 4,4″-diamino-p-terphenyl for side-preferential attachment of 2-triphenylenecarbaldehyde. Our findings provide a new route towards surface-induced dissymmetric activation of a symmetric compound.

6.
Nat Commun ; 9(1): 2420, 2018 06 20.
Artigo em Inglês | MEDLINE | ID: mdl-29925833

RESUMO

Deciphering absolute configuration of a single molecule by direct visual inspection is the next step in compound identification, with far-reaching implications for medicinal chemistry, pharmacology, and natural product synthesis. We demonstrate the feasibility of this approach utilizing low temperature atomic force microscopy (AFM) with a CO-functionalized tip to determine the absolute configuration and orientation of a single, adsorbed [123]tetramantane molecule, the smallest chiral diamondoid. We differentiate between single enantiomers on Cu(111) by direct visual inspection, and furthermore identify molecular dimers and molecular clusters. The experimental results are confirmed by a computational study that allowed quantification of the corresponding intermolecular interactions. The unique toolset of absolute configuration determination combined with AFM tip manipulation opens a route for studying molecular nucleation, including chirality-driven assembly or reaction mechanisms.

7.
J Am Chem Soc ; 140(24): 7526-7532, 2018 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-29750508

RESUMO

Aromatic C-H bond activation has attracted much attention due to its versatile applications in the synthesis of aryl-containing chemicals. The major challenge lies in the minimization of the activation barrier and maximization of the regioselectivity. Here, we report the highly selective activation of the central aromatic C-H bond in meta-aryne species anchored to a copper surface, which catalyzes the C-H bond dissociation. Two prototype molecules, i.e., 4',6'-dibromo- meta-terphenyl and 3',5'-dibromo- ortho-terphenyl, have been employed to perform C-C coupling reactions on Cu(111). The chemical structures of the resulting products have been clarified by a combination of scanning tunneling microscopy and noncontact atomic force microscopy. Both methods demonstrate a remarkable weakening of the targeted C-H bond. Density functional theory calculations reveal that this efficient C-H activation stems from the extraordinary chemisorption of the meta-aryne on the Cu(111) surface, resulting in the close proximity of the targeted C-H group to the Cu(111) surface and the absence of planarity of the phenyl ring. These effects lead to a lowering of the C-H dissociation barrier from 1.80 to 1.12 eV, in agreement with the experimental data.

8.
J Am Chem Soc ; 140(19): 6076-6082, 2018 05 16.
Artigo em Inglês | MEDLINE | ID: mdl-29543446

RESUMO

Hierarchical control of chemical reactions is being considered as one of the most ambitious and challenging topics in modern organic chemistry. In this study, we have realized the one-by-one scission of the X-H bonds (X = N and C) of aromatic amines in a controlled fashion on the Cu(111) surface. Each dehydrogenation reaction leads to certain metal-organic supramolecular structures, which were monitored in single-bond resolution via scanning tunneling microscopy and noncontact atomic force microscopy. Moreover, the reaction pathways were elucidated from X-ray photoelectron spectroscopy measurements and density functional theory calculations. Our insights pave the way for connecting molecules into complex structures in a more reliable and predictable manner, utilizing carefully tuned stepwise on-surface synthesis protocols.

9.
ACS Nano ; 11(9): 9459-9466, 2017 09 26.
Artigo em Inglês | MEDLINE | ID: mdl-28846392

RESUMO

London dispersion (LD) acts between all atoms and molecules in nature, but the role of LD interactions in the self-assembly of molecular layers is still poorly understood. In this study, direct visualization of single molecules using atomic force microscopy with CO-functionalized tips revealed the exact adsorption structures of bulky and highly polarizable [121]tetramantane molecules on Au(111) and Cu(111) surfaces. We determined the absolute molecular orientations of the completely sp3-hybridized tetramantanes on metal surfaces. Moreover, we demonstrate how LD drives this on-surface self-assembly of [121]tetramantane hydrocarbons, resulting in the formation of a highly ordered 2D lattice. Our experimental findings were underpinned by a systematic computational study, which allowed us to quantify the energies associated with LD interactions and to analyze intermolecular close contacts and attractions in detail.

10.
ACS Nano ; 11(4): 4183-4190, 2017 04 25.
Artigo em Inglês | MEDLINE | ID: mdl-28346826

RESUMO

The in-depth knowledge about on-surface reaction mechanisms is crucial for the tailor-made design of covalently bonded organic frameworks, for applications such as nanoelectronic or -optical devices. Latest developments in atomic force microscopy, which rely on functionalizing the tip with single CO molecules at low temperatures, allow to image molecular systems with submolecular resolution. Here, we are using this technique to study the complete reaction pathway of the on-surface Ullmann-type coupling between bromotriphenylene molecules on a Cu(111) surface. All steps of the Ullmann reaction, i.e., bromotriphenylenes, triphenylene radicals, organometallic intermediates, and bistriphenylenes, were imaged with submolecular resolution. Together with density functional theory calculations with dispersion correction, our study allows to address the long-standing question of how the organometallic intermediates are coordinated via Cu surface or adatoms.

11.
Nanoscale ; 7(39): 16298-311, 2015 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-26377347

RESUMO

We present a method to determine the local surface charge of solid-liquid interfaces from Atomic Force Microscopy (AFM) measurements that takes into account shifts of the adsorption/desorption equilibria of protons and ions as the cantilever tip approaches the sample. We recorded AFM force distance curves in dynamic mode with sharp tips on heterogeneous silica surfaces partially covered by gibbsite nano-particles immersed in an aqueous electrolyte with variable concentrations of dissolved NaCl and KCl at pH 5.8. Forces are analyzed in the framework of Derjaguin-Landau-Verwey-Overbeek (DLVO) theory in combination with a charge regulation boundary that describes adsorption and desorption reactions of protons and ions. A systematic method to extract the equilibrium constants of these reactions by simultaneous least-squared fitting to experimental data for various salt concentrations is developed and is shown to yield highly consistent results for silica-electrolyte interfaces. For gibbsite-electrolyte interfaces, the surface charge can be determined, yet, an unambiguous identification of the relevant surface speciation reactions is not possible, presumably due to a combination of intrinsic chemical complexity and heterogeneity of the nano-particle surfaces.

12.
Nanotechnology ; 25(47): 475701, 2014 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-25369864

RESUMO

We present experimental and computational investigations of tetramodal and pentamodal atomic force microscopy (AFM), respectively, whereby the first four or five flexural eigenmodes of the cantilever are simultaneously excited externally. This leads to six to eight additional observables in the form of amplitude and phase signals, with respect to the monomodal amplitude modulation method. We convert these additional observables into three or four dissipation and virial expressions, and show that these quantities can provide enhanced contrast that would otherwise remain hidden in the original observables. We also show that the complexity of the multimodal impact leads to significant energy transfer between the active eigenmodes, such that the dissipated power for individual eigenmodes may be positive or negative, while the total dissipated power remains positive. These results suggest that the contrast of individual eigenmodes in multifrequency AFM should be not be considered in isolation and that it may be possible to use different eigenfrequencies to probe sample properties that respond to different relaxation times.

13.
Beilstein J Nanotechnol ; 5: 1144-51, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-25161847

RESUMO

This paper presents experiments on Nafion(®) proton exchange membranes and numerical simulations illustrating the trade-offs between the optimization of compositional contrast and the modulation of tip indentation depth in bimodal atomic force microscopy (AFM). We focus on the original bimodal AFM method, which uses amplitude modulation to acquire the topography through the first cantilever eigenmode, and drives a higher eigenmode in open-loop to perform compositional mapping. This method is attractive due to its relative simplicity, robustness and commercial availability. We show that this technique offers the capability to modulate tip indentation depth, in addition to providing sample topography and material property contrast, although there are important competing effects between the optimization of sensitivity and the control of indentation depth, both of which strongly influence the contrast quality. Furthermore, we demonstrate that the two eigenmodes can be highly coupled in practice, especially when highly repulsive imaging conditions are used. Finally, we also offer a comparison with a previously reported trimodal AFM method, where the above competing effects are minimized.

14.
Chemistry ; 20(38): 12009-14, 2014 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-25098549

RESUMO

A new type of a bifunctional DNA architecture based on a three way junction is developed that combines the structural motif of sticky perylene bisimide caps with a tris-bipyridyl metal ion lock in the center part. A clear stabilizing effect was observed in the presence of Fe(3+), Ni(2+) and Zn(2+) by the formation of corresponding bipyridyl complexes in the branching part of the DNA three way junctions. The dimerization of the 5'-terminally attached perylene diimides (PDI) chromophores by hydrophobic interactions can be followed by significant changes in the UV/Vis absorption and steady-state fluorescence. The PDI-mediated DNA assembly occurs at temperatures below the melting temperature and is not influenced by the metal-ion bipyridyl locks in the central part. The corresponding AFM images revealed the formation of higher-ordered structures as the result of DNA assemblies mediated by the PDI interactions.


Assuntos
DNA/química , Imidas/química , Metais Pesados/química , Perileno/análogos & derivados , Cátions Bivalentes/química , Dimerização , Compostos Férricos/química , Estrutura Molecular , Níquel/química , Conformação de Ácido Nucleico , Perileno/química , Espectrometria de Fluorescência , Zinco/química
15.
Sci Rep ; 4: 4956, 2014 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-24850566

RESUMO

The distribution of ions and charge at solid-water interfaces plays an essential role in a wide range of processes in biology, geology and technology. While theoretical models of the solid-electrolyte interface date back to the early 20th century, a detailed picture of the structure of the electric double layer has remained elusive, largely because of experimental techniques have not allowed direct observation of the behaviour of ions, i.e. with subnanometer resolution. We have made use of recent advances in high-resolution Atomic Force Microscopy to reveal, with atomic level precision, the ordered adsorption of the mono- and divalent ions that are common in natural environments to heterogeneous gibbsite/silica surfaces in contact with aqueous electrolytes. Complemented by density functional theory, our experiments produce a detailed picture of the formation of surface phases by templated adsorption of cations, anions and water, stabilized by hydrogen bonding.

16.
ACS Nano ; 7(11): 10387-96, 2013 Nov 26.
Artigo em Inglês | MEDLINE | ID: mdl-24131492

RESUMO

Characterization of subsurface morphology and mechanical properties with nanoscale resolution and depth control is of significant interest in soft matter fields like biology, polymer science, and even in future applications like nanomanufacturing, where buried structural and compositional features are important to the functionality of the system. However, controllably "feeling" the subsurface is a challenging task for which the available imaging tools are relatively limited. In this paper, we propose a trimodal atomic force microscopy (AFM) imaging scheme, whereby three eigenmodes of the microcantilever probe are used as separate control "knobs" to simultaneously measure the topography, modulate sample indentation by the tip during tip-sample impact, and map compositional contrast, respectively. We illustrate this multifrequency imaging approach through computational simulation and experiments conducted on ultrathin polymer films with embedded glass nanoparticles in ambient air. By actively increasing the tip-sample indentation using a higher eigenmode of the cantilever, we are able to gradually and controllably reveal glass nanoparticles which are buried tens of nanometers deep under the surface, while still being able to refocus on the surface.


Assuntos
Microscopia de Força Atômica/métodos , Polímeros/química , Materiais Biocompatíveis/química , Simulação por Computador , Dimetilpolisiloxanos/química , Vidro , Cinética , Modelos Teóricos , Nanopartículas/química , Nanotecnologia/métodos , Propriedades de Superfície
17.
Beilstein J Nanotechnol ; 4: 198-207, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-23616939

RESUMO

We present an overview of the bimodal amplitude-frequency-modulation (AM-FM) imaging mode of atomic force microscopy (AFM), whereby the fundamental eigenmode is driven by using the amplitude-modulation technique (AM-AFM) while a higher eigenmode is driven by using either the constant-excitation or the constant-amplitude variant of the frequency-modulation (FM-AFM) technique. We also offer a comparison to the original bimodal AFM method, in which the higher eigenmode is driven with constant frequency and constant excitation amplitude. General as well as particular characteristics of the different driving schemes are highlighted from theoretical and experimental points of view, revealing the advantages and disadvantages of each. This study provides information and guidelines that can be useful in selecting the most appropriate operation mode to characterize different samples in the most efficient and reliable way.

18.
Nanotechnology ; 24(13): 135702, 2013 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-23478354

RESUMO

We present a systematic analysis of the atomic-scale imaging capabilities for mineral surfaces in a liquid environment in single and dual mode amplitude modulation dynamic force microscopy. To study the difference in sensitivity between the first and second eigenmode phase signals we investigate the observed atomic-scale contrasts of the mica-water interface under varying imaging conditions. For this purpose, we systematically change the main imaging parameters including the setpoint amplitude of the imaging feedback, the free oscillation amplitudes of the first and second flexural eigenmodes, and their ratio. This allows for an in-depth analysis of the sensitivities of the first and second eigenmode phase signals to draw conclusions regarding the underlying physical mechanisms and the interpretation of the contrast in the multi-frequency technique.


Assuntos
Interpretação de Imagem Assistida por Computador/métodos , Microscopia de Força Atômica/métodos , Minerais/química , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Substâncias Macromoleculares/química , Teste de Materiais , Conformação Molecular , Tamanho da Partícula , Transição de Fase , Propriedades de Superfície
19.
Angew Chem Int Ed Engl ; 51(26): 6378-82, 2012 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-22644905

RESUMO

Conductive tubes: Self-assembled nanotubes of a bacteriochlorophyll derivative are reminiscent of natural chlorosomal light-harvesting assemblies. After deposition on a substrate that consists of a non-conductive silicon oxide surface (see picture, brown) and contacting the chlorin nanowires to a conductive polymer (yellow), they show exceptional charge-transport properties.


Assuntos
Clorofila/química , Corantes/química , Nanofios/química , Microscopia Crioeletrônica , Íons/química , Microscopia de Força Atômica , Microscopia Eletrônica de Transmissão , Modelos Moleculares , Estrutura Molecular , Nanofios/ultraestrutura
20.
Nanotechnology ; 22(30): 305706, 2011 Jul 29.
Artigo em Inglês | MEDLINE | ID: mdl-21719972

RESUMO

We use atomic force microscopy (AFM) to determine electrostatic interactions between Si tips and Si wafers in aqueous electrolytes of variable composition. We demonstrate that dynamic force spectroscopy (DFS) in the frequency modulation (FM) mode with stiff cantilevers and sharp tips allows for a continuous detection of the tip-sample interactions without mechanical jump-to-contact instability and with substantially higher lateral resolution than standard colloidal probe measurements. For four different species of salt (NaCl, KCl, MgCl(2), CaCl(2)) we find repulsive electrostatic forces at the lowest salt concentrations (1 mM) that become progressively screened until they are dominated by attractive van der Waals forces at the highest concentration (100 mM). For the divalent cations the crossover from repulsive to attractive forces occurs at lower concentrations than for monovalent cations. Surface charges extracted from fits to standard Poisson-Boltzmann double layer theory indicate a rather weak dependence of the surface charge on the ion concentration. The high lateral resolution of our approach is illustrated by a 2D force field measurement over a patterned surface of a supported lipid bilayer on a mica substrate.

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