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1.
Nano Lett ; 21(15): 6391-6397, 2021 Aug 11.
Artigo em Inglês | MEDLINE | ID: mdl-34283625

RESUMO

Using a q+ atomic force microscopy at low temperature, a sexiphenyl molecule is slid across an atomically flat Ag(111) surface along the direction parallel to its molecular axis and sideways to the axis. Despite identical contact area and underlying surface geometry, the lateral force required to move the molecule in the direction parallel to its molecular axis is found to be about half of that required to move it sideways. The origin of the lateral force anisotropy observed here is traced to the one-dimensional shape of the molecule, which is further confirmed by molecular dynamics simulations. We also demonstrate that scanning tunneling microscopy can be used to determine the comparative lateral force qualitatively. The observed one-dimensional lateral force anisotropy may have important implications in atomic scale frictional phenomena on materials surfaces.

2.
J Am Chem Soc ; 143(2): 1224-1234, 2021 01 20.
Artigo em Inglês | MEDLINE | ID: mdl-33395279

RESUMO

Asymmetrical and dissymmetrical structures are widespread and play a critical role in nature and life systems. In the field of metallo-supramolecular assemblies, it is still in its infancy for constructing artificial architectures using dissymmetrical building blocks. Herein, we report the self-assembly of supramolecular systems based on two dissymmetrical double-layered ligands. With the aid of ultra-high-vacuum, low-temperature scanning tunneling microscopy (UHV-LT-STM), we were able to investigate four isomeric structures corresponding to four types of binding modes of ligand LA with two major conformations complexes A. The distribution of isomers measured by STM and total binding energy of each isomer obtained by density functional theory (DFT) calculations suggested that the most abundant isomer could be the most stable one with highest total binding energy. Finally, through shortening the linker between inner and outer layers and the length of arms, the arrangement of dissymmetrical ligand LB could be controlled within one binding mode corresponding to the single conformation for complexes B.

3.
J Am Chem Soc ; 142(34): 14638-14648, 2020 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-32794746

RESUMO

Fluorescent metallosupramolecules have received considerable attention due to their precisely controlled dimensions as well as the tunable photophysical and photochemical properties. However, phosphorescent analogues are still rare and limited to small structures with low-temperature phosphorescence. Herein, we report the self-assembly and photophysical studies of a giant, discrete metallosupramolecular concentric hexagon functionalized with six alkynylplatinum(II) bzimpy moieties. With a size larger than 10 nm and molecular weight higher than 26 000 Da, the assembled terpyridine-based supramolecule displayed phosphorescent emission at room temperature. Moreover, the supramolecule exhibited enhanced aggregation-induced phosphorescent emission compared to the ligand by tuning the aggregation states through intermolecular interactions and significant enhancement of emission to CO2 gas.

4.
ACS Nano ; 14(7): 8887-8893, 2020 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-32574034

RESUMO

Charge density waves have been intensely studied in inorganic materials such as transition metal dichalcogenides; however their counterpart in organic materials has yet to be explored in detail. Here we report the finding of robust two-dimensional charge density waves in molecular layers formed by α-(BEDT-TTF)2-I3 on a Ag(111) surface. Low-temperature scanning tunneling microscopy images of a multilayer thick α-(BEDT-TTF)2-I3 on a Ag(111) substrate reveal the coexistence of 5a0 × 5a0 and 31a0×31a0 R9° charge density wave patterns commensurate with the underlying molecular lattice at 80 K. Both charge density wave patterns remain in nanosize molecular islands with just a single constituent molecular-layer thickness at 80 and 5 K. Local tunneling spectroscopy measurements reveal the variation of the gap from 244 to 288 meV between the maximum and minimum charge density wave locations. Density functional theory calculations further confirm a vertical positioning of BEDT-TTF molecules in the molecular layer. While the observed charge density wave patterns are stable for the defect sites, they can be reversibly switched for one molecular lattice site by means of inelastic tunneling electron energy transfer with the electron energies exceeding 400 meV using a scanning tunneling microscope manipulation scheme.

5.
J Synchrotron Radiat ; 27(Pt 3): 836-843, 2020 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-32381788

RESUMO

In recent years, there have been numerous efforts worldwide to develop the synchrotron X-ray scanning tunneling microscopy (SX-STM) technique. Here, the inauguration of XTIP, the world's first beamline fully dedicated to SX-STM, is reported. The XTIP beamline is located at Sector 4 of the Advanced Photon Source at Argonne National Laboratory. It features an insertion device that can provide left- or right-circular as well as horizontal- and vertical-linear polarization. XTIP delivers monochromatic soft X-rays of between 400 and 1900 eV focused into an environmental enclosure that houses the endstation instrument. This article discusses the beamline system design and its performance.

6.
Nat Chem ; 12(6): 579, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32409723

RESUMO

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

7.
J Am Chem Soc ; 142(21): 9809-9817, 2020 05 27.
Artigo em Inglês | MEDLINE | ID: mdl-32311259

RESUMO

Coordination-driven self-assembly has been extensively employed to construct a variety of discrete structures as a bottom-up strategy. However, mechanistic understanding regarding whether self-assembly is under kinetic or thermodynamic control is less explored. To date, such mechanistic investigation has been limited to distinct, assembled structures. It still remains a formidable challenge to study the kinetic and thermodynamic behavior of self-assembly systems with multiple assembled isomers due to the lack of characterization methods. Herein, we use a stepwise strategy which combined self-recognition and self-assembly processes to construct giant metallo-supramolecules with 8 positional isomers in solution. With the help of ultrahigh-vacuum, low-temperature scanning tunneling microscopy and scanning tunneling spectroscopy, we were able to unambiguously differentiate 14 isomers on the substrate which correspond to 8 isomers in solution. Through measurement of 162 structures, the experimental probability of each isomer was obtained and compared with the theoretical probability. Such a comparison along with density functional theory (DFT) calculation suggested that although both kinetic and thermodynamic control existed in this self-assembly, the increased experimental probabilities of isomers compared to theoretical probabilities should be attributed to thermodynamic control.


Assuntos
Complexos de Coordenação/química , Termodinâmica , Complexos de Coordenação/síntese química , Teoria da Densidade Funcional , Cinética , Substâncias Macromoleculares/síntese química , Substâncias Macromoleculares/química , Microscopia de Tunelamento , Estrutura Molecular
8.
Nat Chem ; 12(5): 468-474, 2020 05.
Artigo em Inglês | MEDLINE | ID: mdl-32284575

RESUMO

For the past three decades, the coordination-driven self-assembly of three-dimensional structures has undergone rapid progress; however, parallel efforts to create large discrete two-dimensional architectures-as opposed to polymers-have met with limited success. The synthesis of metallo-supramolecular systems with well-defined shapes and sizes in the range of 10-100 nm remains challenging. Here we report the construction of a series of giant supramolecular hexagonal grids, with diameters on the order of 20 nm and molecular weights greater than 65 kDa, through a combination of intra- and intermolecular metal-mediated self-assembly steps. The hexagonal intermediates and the resulting self-assembled grid architectures were imaged at submolecular resolution by scanning tunnelling microscopy. Characterization (including by scanning tunnelling spectroscopy) enabled the unambiguous atomic-scale determination of fourteen hexagonal grid isomers.


Assuntos
Complexos de Coordenação/química , Estruturas Metalorgânicas/química , Metais/química , Nanoestruturas/química , Isomerismo , Ligantes , Microscopia de Tunelamento , Modelos Moleculares , Estrutura Molecular , Peso Molecular
9.
J Am Chem Soc ; 142(13): 6196-6205, 2020 04 01.
Artigo em Inglês | MEDLINE | ID: mdl-32150680

RESUMO

During the past few decades, the study of the single polymer chain has attracted considerable attention with the goal of exploring the structure-property relationship of polymers. It still, however, remains challenging due to the variability and low atomic resolution of the amorphous single polymer chain. Here, we demonstrated a new strategy to visualize the single metallopolymer chain with a hexameric or trimeric supramolecule as a repeat unit, in which Ru(II) with strong coordination and Fe(II) with weak coordination were combined together in a stepwise manner. With the help of ultrahigh-vacuum, low-temperature scanning tunneling microscopy (UHV-LT-STM) and scanning tunneling spectroscopy (STS), we were able to directly visualize both Ru(II) and Fe(II), which act as staining reagents on the repeat units, thus providing detailed structural information for the single polymer chain. As such, the direct visualization of the single random polymer chain is realized to enhance the characterization of polymers at the single-molecule level.


Assuntos
Complexos de Coordenação/química , Ferro/química , Polímeros/química , Rutênio/química , Técnicas de Química Sintética , Complexos de Coordenação/síntese química , Microscopia de Tunelamento , Polímeros/síntese química
10.
Nanoscale ; 11(46): 22351-22358, 2019 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-31728463

RESUMO

Charge density waves and negative differential resistance are seemingly unconnected physical phenomena. The former is an ordered quantum fluid of electrons, intensely investigated for its relation with superconductivity, while the latter receives much attention for its potential applications in electronics. Here we show that these two phenomena can not only coexist but also that the localized electronic states of the charge density wave are essential to induce negative differential resistance in a transition metal dichalcogenide, 1T-TaS2. Using scanning tunneling microscopy and spectroscopy, we report the observation of negative differential resistance in the commensurate charge density wave state of 1T-TaS2. The observed phenomenon is explained by the interplay of interlayer and intra-layer tunneling with the participation of the atomically localized states of the charge density wave maxima and minima. We demonstrate that lattice defects can locally affect the coupling between the layers and are therefore a mechanism to realize NDR in these materials.

11.
Nat Commun ; 10(1): 3742, 2019 Aug 20.
Artigo em Inglês | MEDLINE | ID: mdl-31431627

RESUMO

Synthetic molecular machines designed to operate on materials surfaces can convert energy into motion and they may be useful to incorporate into solid state devices. Here, we develop and characterize a multi-component molecular propeller that enables unidirectional rotations on a material surface when energized. Our propeller is composed of a rotator with three molecular blades linked via a ruthenium atom to a ratchet-shaped molecular gear. Upon adsorption on a gold crystal surface, the two dimensional nature of the surface breaks the symmetry and left or right tilting of the molecular gear-teeth induces chirality. The molecular gear dictates the rotational direction of the propellers and step-wise rotations can be induced by applying an electric field or using inelastic tunneling electrons from a scanning tunneling microscope tip. By means of scanning tunneling microscope manipulation and imaging, the rotation steps of individual molecular propellers are directly visualized, which confirms the unidirectional rotations of both left and right handed molecular propellers into clockwise and anticlockwise directions respectively.

12.
J Am Chem Soc ; 141(33): 13187-13195, 2019 08 21.
Artigo em Inglês | MEDLINE | ID: mdl-31345024

RESUMO

Multicomponent self-assembly in one pot provides an efficient way for constructing complex architectures using multiple types of building blocks with different levels of interactions orthogonally. The preparation of multiple types of building blocks typically includes tedious synthesis. Here, we developed a multicomponent synthesis/self-assembly strategy, which combined covalent interaction (C-N bond, formed through condensation of pyrylium salt with primary amine) and metal-ligand interaction (N → Zn bond, formed through 2,2':6',2″-terpyridine-Zn coordination) in one pot. The high compatibility of this pair of interactions smoothly and efficiently converted three and four types of components into the desired complex structures, which are supramolecular Kandinsky Circles and spiderwebs, respectively.


Assuntos
Complexos de Coordenação/síntese química , Piridinas/síntese química , Zinco/química , Técnicas de Química Combinatória , Complexos de Coordenação/química , Compostos Heterocíclicos com 3 Anéis/síntese química , Compostos Heterocíclicos com 3 Anéis/química , Ligantes , Piridinas/química , Sais/síntese química , Sais/química
13.
Nanoscale ; 11(31): 14698-14706, 2019 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-31343043

RESUMO

Two-dimensional (2D) materials provide a plethora of novel condensed matter physics and are the new playground in materials science, offering potentially vast applications. One of the critical hurdles for many 2D systems is the synthesis of these low-dimensional systems as well as the prediction and identification of new candidates. Herein, a self-assembly of a monolayer tellurene by bonding CdTe wafers is demonstrated for the first time. The conventional applications of wafer-bonding range from the production of microelectromechanical systems to the synthesis of lattice-mismatched multi-junction photovoltaics. Due to the heterogeneous materials that are typically employed, the bond-interface usually contains a thin amorphous layer or arrays of dislocations. Such an interface is thus itself inactive and in many cases has detrimental effects on the device. The new material phase stabilized in this work consists of an undulating monolayer of tellurium atoms covalently bonded to {111} Cd-terminated CdTe wafer surfaces. First-principles calculations and experimentally observed changes in the localized plasmon excitation energy indicate the clear rearrangement of the underlying band-structure suggesting a metallic character, bands showing linear dispersion, and a significant asymmetric spin-band splitting. The I-V characteristics show the presence of a highly conductive pathway that lowers the resistivity by three orders of magnitude, as compared to bulk CdTe, which can be attributed to the tellurium monolayer. The findings indicate that suitably chosen crystallographic wafer surfaces can act as structural templates allowing the production of exotic phases. The presently stabilized monolayer is an addition to the family of tellurene variants, providing new insights into the fundamental properties of this and other emerging 2D materials, while attracting attention to the unusual side of the wafer-bonding technology exemplified in this study.

14.
ACS Nano ; 13(7): 8284-8291, 2019 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-31268680

RESUMO

The ability to control nanoscale electronic properties by introducing macroscopic strain is of critical importance for the implementation of two-dimensional (2D) materials into flexible electronics and next-generation strain engineering devices. In this work, we correlate the atomic-scale lattice deformation with a systematic macroscopic bending of monolayer molybdenum disulfide films by using scanning tunneling microscopy and spectroscopy implemented with a custom-built sample holder to control the strain. Using this technique, we are able to induce strains of up to 3% before slipping effects take place and relaxation mechanisms prevail. We find a reduction of the quasiparticle bandgap of about 400 meV per percent local strain measured with a minimum gap of 1.2 eV. Furthermore, unintentional nanoscale strain relaxation of van der Waals monolayer sheets can negatively impact strain engineered device performance. Here we investigate such strain relaxation mechanisms that include one-dimensional ripples and 2D wrinkles which alter the spatial electronic density of states and strain distribution on the atomic scale.

15.
Adv Mater ; 31(11): e1807178, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30680821

RESUMO

In the continuously growing field of correlated electronic molecular crystals, there is significant interest in addressing alkali-metal-intercalated aromatic hydrocarbons, in which the possibility of high-temperature superconductivity emerges. However, searching for superconducting aromatic molecular crystals remains elusive due to their small shielding fraction volume. To exploit this potential, a design principle for percolation networks of technologically important film geometry is indispensable. Here the effect of potassium-intercalation is shown on the percolation network in self-assembled aromatic molecular crystals. It is demonstrated that one-dimensional (1D) dipole pairs, induced by dipole interaction, regulate the conductivity, as well as the electronic and optical transitions, in alkali-metal-intercalated molecular electronic crystals. A solid-solution growth methodology of aromatic molecular films with a broad range of stability is developed to uncover electronic and optical transitions of technological importance. The light-induced electron interactions enhance the charge-carrier itinerancy, leading to a switchable metal-to-insulator transition. This discovery opens a route for the development of aromatic molecular electronic solids and long-term modulation of electronic efficacy in nanotechnologically important thin films.

16.
ACS Nano ; 12(1): 217-225, 2018 01 23.
Artigo em Inglês | MEDLINE | ID: mdl-29236480

RESUMO

Carotenoids and chlorophyll are essential parts of plant leaves and are involved in photosynthesis, a vital biological process responsible for the origin of life on Earth. Here, we investigate how ß-carotene and chlorophyll-a form mixed molecular phases on a Au(111) surface using low-temperature scanning tunneling microscopy and molecular manipulation at the single-molecule level supported by density functional theory calculations. By isolating individual molecules from nanoscale molecular clusters with a scanning tunneling microscope tip, we are able to identify five ß-carotene conformations including a structure exhibiting a three-dimensional conformation. Furthermore, molecular resolution images enable direct visualization of ß-carotene/chlorophyll-a clsuters, with intimate structural details highlighting how they pair: ß-carotene preferentially positions next to chlorophyll-a and induces switching of chlorophyll-a from straight to several bent tail conformations in the molecular clusters.


Assuntos
Clorofila A/química , Microscopia de Tunelamento/métodos , beta Caroteno/química , Ouro/química , Modelos Moleculares , Conformação Molecular , Propriedades de Superfície
17.
Nat Commun ; 8(1): 946, 2017 10 16.
Artigo em Inglês | MEDLINE | ID: mdl-29038513

RESUMO

Kondo resonances in heterostructures formed by magnetic molecules on a metal require free host electrons to interact with the molecular spin and create delicate many-body states. Unlike graphene, semiconducting graphene nanoribbons do not have free electrons due to their large bandgaps, and thus they should electronically decouple molecules from the metal substrate. Here, we observe unusually well-defined Kondo resonances in magnetic molecules separated from a gold surface by graphene nanoribbons in vertically stacked heterostructures. Surprisingly, the strengths of Kondo resonances for the molecules on graphene nanoribbons appear nearly identical to those directly adsorbed on the top, bridge and threefold hollow sites of Au(111). This unexpectedly strong spin-coupling effect is further confirmed by density functional calculations that reveal no spin-electron interactions at this molecule-gold substrate separation if the graphene nanoribbons are absent. Our findings suggest graphene nanoribbons mediate effective spin coupling, opening a way for potential applications in spintronics.Semiconducting graphene nanoribbon provides a platform for band-gap engineering desired for electronic and optoelectronic applications. Here, Li et al. show that graphene nanoribbon can effectively mediate the interaction of molecular magnetic moment and electronic spin in underlying metallic substrates.

18.
Langmuir ; 32(15): 3587-600, 2016 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-26991048

RESUMO

9-(Bis-p-tert-octylphenyl)-amino-perylene-3,4-dicarboxy anhydride (BOPA-PDCA) is a strongly dipolar molecule representing a group of asymmetrically substituted perylenes that are employed in dye-sensitized solar cells and hold great promise for discotic liquid crystal applications. Thin BOPA-PDCA films with orientated dipole moments can potentially be used to tune the energy-level alignment in electronic devices and store information. To help assessing these prospects, we here elucidate the molecular self-assembly and electronic structure of BOPA-PCDA employing room temperature scanning tunneling microscopy and spectroscopy in combination with ultraviolet and X-ray photoelectron spectroscopies. BOPA-PCDA monolayers on Au(111) exclusively form in-plane antiferroelectric phases. The molecular arrangements, the increase of the average number of molecules per unit cell via ripening, and the rearrangement upon manipulation with the STM tip indicate an influence of the dipole moment on the molecular assembly and the rearrangement. A slightly preferred out-of-plane orientation of the molecules in the multilayer induces a surface potential of 1.2 eV. This resembles the giant surface potential effect that was reported for vacuum-deposited tris(8-hydroxyquinoline)aluminum and deemed applicable for data storage. Notably, the surface potential in the case of BOPA-PDCA can in part be reversibly removed by visible light irradiation.

19.
J Synchrotron Radiat ; 23(2): 574-8, 2016 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-26917146

RESUMO

Localized spectroscopy with simultaneous topographic, elemental and magnetic information is presented. A synchrotron X-ray scanning tunneling microscope has been employed for the local study of the X-ray magnetic circular dichroism at the Fe L2,3-edges of a thin iron film grown on Cu(111). Polarization-dependent X-ray absorption spectra have been obtained through a tunneling smart tip that serves as a photoelectron detector. In contrast to conventional spin-polarized scanning tunneling microscopy, X-ray excitations provide magnetic contrast even with a non-magnetic tip. Intensity variations in the photoexcited tip current point to chemical variations within a single magnetic Fe domain.

20.
ACS Nano ; 9(9): 8644-6, 2015 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-26325629

RESUMO

Engineering of supramolecular assemblies on surfaces is an emerging field of research impacting chemistry, electronics, and biology. Among supramolecular assemblies, metal-containing structures provide rich properties and enable robust nanostructured designs. In this issue of ACS Nano, Feng et al. report that supramolecular assemblies can trap gold adatoms that maintain a charged state on a Au(111) surface. Such charged adatoms may offer additional degrees of freedom in designing novel supramolecular architectures for efficient catalysts, memory, and charge storage for medical applications.

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