Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 76
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
Angew Chem Int Ed Engl ; 60(1): 439-445, 2021 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-32886405

RESUMO

Recently π-d conjugated coordination polymers have received a lot of attention owing to their unique material properties, although synthesis of long and defect-free polymers remains challenging. Herein we introduce a novel on-surface synthesis of coordination polymers with quinoidal ligands under ultra-high vacuum conditions, which enables formation of flexible coordination polymers with lengths up to hundreds of nanometers. Moreover, this procedure allows the incorporation of different transition-metal atoms with four- or two-fold coordination. Remarkably, the two-fold coordination mode revealed the formation of wires constituted by (electronically) independent 12-membered antiaromatic macrocycles linked together through two C-C single bonds.

2.
J Phys Chem Lett ; : 330-336, 2020 Dec 22.
Artigo em Inglês | MEDLINE | ID: mdl-33352044

RESUMO

Polycyclic aromatic hydrocarbons (PAHs) are a family of organic compounds comprising two or more fused aromatic rings which feature manifold applications in modern technology. Among these species, those presenting an open-shell magnetic ground state are of particular interest for organic electronic, spintronic, and non-linear optics and energy storage devices. Within PAHs, special attention has been devoted in recent years to the synthesis and study of the acene and fused acene (periacene) families, steered by their decreasing HOMO-LUMO gap with length and predicted open-shell character above some size. However, an experimental fingerprint of such magnetic ground state has remained elusive. Here, we report on the in-depth electronic characterization of isolated peripentacene molecules on a Au(111) surface. Scanning tunnelling spectroscopy, complemented by computational investigations, reveals an antiferromagnetic singlet ground state, characterized by singlet-triplet inelastic excitations with an experimental effective exchange coupling (Jeff) of 40.5 meV. Our results deepen the fundamental understanding of organic compounds with magnetic ground states, featuring perspectives in carbon-based spintronic devices.

3.
Nano Lett ; 2020 Dec 11.
Artigo em Inglês | MEDLINE | ID: mdl-33305570

RESUMO

The ability to engineer geometrically well-defined antidots in large triangulene homologues allows for creating an entire family of triangulene quantum rings (TQRs) with tunable high-spin ground state, crucial for next-generation molecular spintronic devices. Herein, we report the synthesis of an open-shell [7]triangulene quantum ring ([7]TQR) molecule on Au(111) through the surface-assisted cyclodehydrogenation of a rationally designed kekulene derivative. Bond-resolved scanning tunneling microscopy (BR-STM) unambiguously imaged the molecular backbone of a single [7]TQR with a triangular zigzag edge topology, which can be viewed as [7]triangulene decorated with a coronene-like antidot in the center. Additionally, dI/dV mapping reveals that both inner and outer zigzag edges contribute to the edge-localized and spin-polarized electronic states of [7]TQR. Both experimental results and spin-polarized density functional theory calculations indicate that [7]TQR retains its open-shell septuple ground state (S = 3) on Au(111). This work demonstrates a new route for the design of high-spin graphene quantum rings for future quantum devices.

4.
Chem Commun (Camb) ; 56(97): 15309-15312, 2020 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-33200161

RESUMO

On-surface synthesis has recently become an essential approach toward the formation of carbon-based nanostructures. Special emphasis is set on the synthesis of π-conjugated polymers taking into consideration their relevance and potential in organic electronics, optoelectronics and spintronics. Here, we report the on-surface synthesis of conjugated ladder polymers consisting of pentacene units doubly-linked via ethynylene-like bonds on the Au(111) surface under ultra-high vacuum conditions. To this aim, we have sublimed pentacene-like precursors equipped with four :CBr2 functional groups to steer the desired reaction upon annealing on the surface. The atomically precise structure of the obtained polymers has been unambiguously characterized via low-temperature scanning tunneling microscopy and non-contact atomic force microscopy. In addition, scanning tunneling spectroscopy complemented with density-functional theory calculations reveal the narrow bandgap of the polymer. Our results provide potential for the synthesis of π-conjugated polymers with prospects in functional carbon-based nanomaterials that exploit multiple connections between molecular backbones.

5.
Nat Commun ; 11(1): 4567, 2020 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-32917869

RESUMO

The development of synthetic strategies to engineer π-conjugated polymers is of paramount importance in modern chemistry and materials science. Here we introduce a synthetic protocol based on the search for specific vibrational modes through an appropriate tailoring of the π-conjugation of the precursors, in order to increase the attempt frequency of a chemical reaction. First, we design a 1D π-conjugated polymer on Au(111), which is based on bisanthene monomers linked by cumulene bridges that tune specific vibrational modes. In a second step, upon further annealing, such vibrational modes steer the twofold cyclization reaction between adjacent bisanthene moieties, which gives rise to a long pentalene-bridged conjugated ladder polymer featuring a low bandgap. In addition, high resolution atomic force microscopy allows us to identify by atomistic insights the resonance form of the polymer, thus confirming the validity of the Glidewell and Lloyd´s rules for aromaticity. This on-surface synthetic strategy may stimulate exploiting previously precluded reactions towards π-conjugated polymers with specific structures and properties.

6.
Chem Commun (Camb) ; 56(61): 8659-8662, 2020 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-32602478

RESUMO

We report a multi-step on-surface synthesis strategy. The first step consists in the surface-supported synthesis of metal-organic complexes, which are subsequently used to steer on-surface alkyne coupling reactions. In addition, we analyze and compare the electronic properties of the different coupling motifs obtained.

7.
ACS Nano ; 2020 Jul 24.
Artigo em Inglês | MEDLINE | ID: mdl-32687321

RESUMO

Functionalization of surfaces with derivatives of Buckminsterfullerene fragment molecules seems to be a promising approach toward bottom-up fabrication of carbon nanotube modified electrode surfaces. The modification of a Cu(100) surface with molecules of the buckybowl pentaindenocorannulene has been studied by means of scanning tunneling microscopy, carbon monoxide-modified noncontact atomic force microscopy, time-of-flight secondary mass spectrometry, and quantum chemical calculations. Two different adsorbate modes are identified, in which the majority is oriented such that the bowl cavity points away from the surface and the convex side is partially immersed into a four-atom vacancy in the Cu(100) surface. A minority is oriented such that the convex side points away from the surface with the five benzo tabs oriented basically parallel to the surface. Thermal annealing leads to hydrogenation and planarization of the molecules in two steps under specific C-C bond cleavage. The benzo tabs of the convex side up species serve as a hydrogen source. The final product has an open-shell electron structure that is quenched on the surface.

8.
ACS Nano ; 14(7): 8931-8938, 2020 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-32539338

RESUMO

The ability to control the emission from single-molecule quantum emitters is an important step toward their implementation in optoelectronic technology. Phthalocyanine and derived metal complexes on thin insulating layers studied by scanning tunneling microscope-induced luminescence (STML) offer an excellent playground for tuning their excitonic and electronic states by Coulomb interaction and to showcase their high environmental sensitivity. Copper phthalocyanine (CuPc) has an open-shell electronic structure, and its lowest-energy exciton is a doublet, which brings interesting prospects in its application for optospintronic devices. Here, we demonstrate that the excitonic state of a single CuPc molecule can be reproducibly switched by atomic-scale manipulations permitting precise positioning of the molecule on the NaCl ionic crystal lattice. Using a combination of STML, AFM, and ab initio calculations, we show the modulation of electronic and optical bandgaps and the exciton binding energy in CuPc by tens of meV. We explain this effect by spatially dependent Coulomb interaction occurring at the molecule-insulator interface, which tunes the local dielectric environment of the emitter.

9.
Artigo em Inglês | MEDLINE | ID: mdl-32592432

RESUMO

We report on the synthesis and characterization of atomically precise one-dimensional diradical peripentacene polymers on a Au(111) surface. By means of high-resolution scanning probe microscopy complemented by theoretical simulations, we provide evidence of their magnetic properties, which arise from the presence of two unpaired spins at their termini. Additionally, we probe a transition of their magnetic properties related to the length of the polymer. Peripentacene dimers exhibit an antiferromagnetic (S=0) singlet ground state. They are characterized by singlet-triplet spin-flip inelastic excitations with an effective exchange coupling (Jeff ) of 2.5 meV, whereas trimers and longer peripentacene polymers reveal a paramagnetic nature and feature Kondo fingerprints at each terminus due to the unpaired spin. Our work provides access to the precise fabrication of polymers featuring diradical character which are potentially useful in carbon-based optoelectronics and spintronics.

10.
ACS Nano ; 14(6): 7269-7279, 2020 Jun 23.
Artigo em Inglês | MEDLINE | ID: mdl-32413259

RESUMO

Understanding the nucleation and growth kinetics of thin films is a prerequisite for their large-scale utilization in devices. For self-assembled molecular phases near thermodynamic equilibrium the nucleation-growth kinetic models are still not developed. Here, we employ real-time low-energy electron microscopy (LEEM) to visualize a phase transformation induced by the carboxylation of 4,4'-biphenyl dicarboxylic acid on Ag(001) under ultra-high-vacuum conditions. The initial (α) and transformed (ß) molecular phases are characterized in detail by X-ray photoemission spectroscopy, single-domain low-energy electron diffraction, room-temperature scanning tunneling microscopy, noncontact atomic force microscopy, and density functional theory calculations. The phase transformation is shown to exhibit a rich variety of phenomena, including Ostwald ripening of the α domains, burst nucleation of the ß domains outside the α phase, remote dissolution of the α domains by nearby ß domains, and a structural change from disorder to order. We show that all phenomena are well described by a general growth-conversion-growth (GCG) model. Here, the two-dimensional gas of admolecules has a dual role: it mediates mass transport between the molecular islands and hosts a slow deprotonation reaction. Further, we conclude that burst nucleation is consistent with a combination of rather weak intermolecular bonding and the onset of an additional weak many-body attractive interaction when a molecule is surrounded by its nearest neighbors. In addition, we conclude that Ostwald ripening and remote dissolution are essentially the same phenomenon, where a more stable structure grows at the expense of a kinetically formed, less stable entity via transport through the 2D gas. The proposed GCG model is validated through kinetic Monte Carlo (kMC) simulations.

11.
Nat Nanotechnol ; 15(6): 437-443, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32313219

RESUMO

Topological band theory predicts that a topological electronic phase transition between two insulators must proceed via closure of the electronic gap. Here, we use this transition to circumvent the instability of metallic phases in π-conjugated one-dimensional (1D) polymers. By means of density functional theory, tight-binding and GW calculations, we predict polymers near the topological transition from a trivial to a non-trivial quantum phase. We then use on-surface synthesis with custom-designed precursors to make polymers consisting of 1D linearly bridged acene moieties, which feature narrow bandgaps and in-gap zero-energy edge states when in the topologically non-trivial phase close to the topological transition point. We also reveal the fundamental connection between topological classes and resonant forms of 1D π-conjugated polymers.

12.
Nat Commun ; 11(1): 1337, 2020 03 12.
Artigo em Inglês | MEDLINE | ID: mdl-32165626

RESUMO

Intramolecular charge transfer processes play an important role in many biological, chemical and physical processes including photosynthesis, redox chemical reactions and electron transfer in molecular electronics. These charge transfer processes are frequently influenced by the dynamics of their molecular or atomic environments, and they are accompanied with energy dissipation into this environment. The detailed understanding of such processes is fundamental for their control and possible exploitation in future technological applications. Most of the experimental studies of the intramolecular charge transfer processes so far have been carried out using time-resolved optical spectroscopies on large molecular ensembles. This hampers detailed understanding of the charge transfer on the single molecular level. Here we build upon the recent progress in scanning probe microscopy, and demonstrate the control of mixed valence state. We report observation of single electron transfer between two ferrocene redox centers within a single molecule and the detection of energy dissipation associated with the single electron transfer.

13.
Angew Chem Int Ed Engl ; 59(15): 6207-6212, 2020 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-31965698

RESUMO

Among the prerequisites for the progress of single-molecule-based electronic devices are a better understanding of the electronic properties at the individual molecular level and the development of methods to tune the charge transport through molecular junctions. Scanning tunneling microscopy (STM) is an ideal tool not only for the characterization, but also for the manipulation of single atoms and molecules on surfaces. The conductance through a single molecule can be measured by contacting the molecule with atomic precision and forming a molecular bridge between the metallic STM tip electrode and the metallic surface electrode. The parameters affecting the conductance are mainly related to their electronic structure and to the coupling to the metallic electrodes. Here, the experimental and theoretical analyses are focused on single tetracenothiophene molecules and demonstrate that an in situ-induced direct desulfurization reaction of the thiophene moiety strongly improves the molecular anchoring by forming covalent bonds between molecular carbon and copper surface atoms. This bond formation leads to an increase of the conductance by about 50 % compared to the initial state.

14.
Angew Chem Int Ed Engl ; 58(51): 18591-18597, 2019 Dec 16.
Artigo em Inglês | MEDLINE | ID: mdl-31608578

RESUMO

The ability to use mechanical strain to steer chemical reactions creates completely new opportunities for solution- and solid-phase synthesis of functional molecules and materials. However, this strategy is not readily applied in the bottom-up on-surface synthesis of well-defined nanostructures. We report an internal strain-induced skeletal rearrangement of one-dimensional (1D) metal-organic chains (MOCs) via a concurrent atom shift and bond cleavage on Cu(111) at room temperature. The process involves Cu-catalyzed debromination of organic monomers to generate 1,5-dimethylnaphthalene diradicals that coordinate to Cu adatoms, forming MOCs with both homochiral and heterochiral naphthalene backbone arrangements. Bond-resolved non-contact atomic force microscopy imaging combined with density functional theory calculations showed that the relief of substrate-induced internal strain drives the skeletal rearrangement of MOCs via 1,3-H shifts and shift of Cu adatoms that enable migration of the monomer backbone toward an energetically favorable registry with the Cu(111) substrate. Our findings on this strain-induced structural rearrangement in 1D systems will enrich the toolbox for on-surface synthesis of novel functional materials and quantum nanostructures.

15.
Chem Commun (Camb) ; 55(71): 10595-10598, 2019 Aug 29.
Artigo em Inglês | MEDLINE | ID: mdl-31423500

RESUMO

Chiral recognition among three differently functionalized heptahelicene derivatives on Ag(111) and Au(111) surfaces has been studied with scanning tunnelling microscopy. All three species were found to self-assemble into racemic zigzag structures, with alternation of (M)- and (P)-enantiomers.

16.
Nanoscale ; 11(33): 15567-15575, 2019 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-31402370

RESUMO

Over the last decades, organosulfur compounds at the interface of noble metals have proved to be extremely versatile systems for both fundamental and applied research. However, the anchoring of thiols to gold remained an object of controversy for a long time. The RS-Au-SR linkage, in particular, is a robust bonding configuration that displays interesting properties. It is generated spontaneously at room temperature and can be used for the production of extended molecular nanostructures. In this work we explore the behavior of 1,4-bis(4-mercaptophenyl)benzene (BMB) on the Au(111) surface, which results in the formation of 2D crystalline metal-organic assemblies stabilized by this type of Au-thiolate bonds. We show how to control the thiolate's stereospecific bonding motif and thereby choose whether to form ordered arrays of Au3BMB3 units with embedded triangular nanopores or linearly stacked metal-organic chains. The former turn out to be thermodynamically favored structures and display confinement of the underneath Au(111) surface state. The electronic properties of single molecules as well as of the 2D crystalline self-assemblies have been characterized both on the metal-organic backbone and inside the associated pores.

17.
Sci Adv ; 5(7): eaav7717, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31360763

RESUMO

The zigzag-edged triangular graphene molecules (ZTGMs) have been predicted to host ferromagnetically coupled edge states with the net spin scaling with the molecular size, which affords large spin tunability crucial for next-generation molecular spintronics. However, the scalable synthesis of large ZTGMs and the direct observation of their edge states have been long-standing challenges because of the molecules' high chemical instability. Here, we report the bottom-up synthesis of π-extended [5]triangulene with atomic precision via surface-assisted cyclodehydrogenation of a rationally designed molecular precursor on metallic surfaces. Atomic force microscopy measurements unambiguously resolve its ZTGM-like skeleton consisting of 15 fused benzene rings, while scanning tunneling spectroscopy measurements reveal edge-localized electronic states. Bolstered by density functional theory calculations, our results show that [5]triangulenes synthesized on Au(111) retain the open-shell π-conjugated character with magnetic ground states.

18.
Nanoscale ; 11(26): 12695-12703, 2019 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-31240287

RESUMO

The interplay of adsorption geometry and interface dipoles of the transition-metal complex Ir(ppy)3 on Cu(111) was studied using low-temperature scanning probe microscopy and density-functional-theory calculations. We find that the orientation of the molecule's intrinsic dipole moment with respect to the surface has a strong influence on the total energy of the different configurations, where the most stable one has the molecular dipole moment pointing out of the surface plane along the surface normal. Adsorption-induced redistribution of charges results in an additional dipole moment that also points out of the surface plane for all configurations. Submolecularly resolved maps of the resulting local contact potential difference suggest that any in-plane dipole moment is very effectively screened.

19.
Angew Chem Int Ed Engl ; 58(20): 6559-6563, 2019 May 13.
Artigo em Inglês | MEDLINE | ID: mdl-30761719

RESUMO

Engineering low-band-gap π-conjugated polymers is a growing area in basic and applied research. The main synthetic challenge lies in the solubility of the starting materials, which precludes advancements in the field. Here, we report an on-surface synthesis protocol to overcome such difficulties and produce poly(p-anthracene ethynylene) molecular wires on Au(111). To this aim, a quinoid anthracene precursor with =CBr2 moieties is deposited and annealed to 400 K, resulting in anthracene-based polymers. High-resolution nc-AFM measurements confirm the nature of the ethynylene-bridge bond between the anthracene moieties. Theoretical simulations illustrate the mechanism of the chemical reaction, highlighting three major steps: dehalogenation, diffusion of surface-stabilized carbenes, and homocoupling, which enables the formation of an ethynylene bridge. Our results introduce a novel chemical protocol to design π-conjugated polymers based on oligoacene precursors and pave new avenues for advancing the emerging field of on-surface synthesis.

20.
Beilstein J Nanotechnol ; 10: 315-321, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-30800570

RESUMO

We investigate the possibility of functionalizing Au tips by N2O molecules deposited on a Au(111) surface and their further use for imaging with submolecular resolution. First, we characterize the adsorption of the N2O species on Au(111) by means of atomic force microscopy with CO-functionalized tips and density functional theory (DFT) simulations. Subsequently we devise a method of attaching a single N2O to a metal tip apex and benchmark its high-resolution imaging and spectroscopic capabilities using FePc molecules. Our results demonstrate the feasibility of high-resolution imaging. However, we find an inherent asymmetry of the N2O probe-particle adsorption on the tip apex, in contrast to a CO tip reference. These findings are consistent with DFT calculations of the N2O- and CO tip apexes.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA