Scanning tunneling microscopy of self-assembled phenylene ethynylene oligomers on Au(111) substrates

In this paper, we report the self-assembly, electrical characterization, and surface modification of dithiolated phenylene-ethynylene oligomer monolayers on a Au(111) surface. The self-assembly was accomplished by thiol bonding the molecules from solution to a Au(111) surface. We have confirmed the formation of self-assembled monolayers by scanning tunneling microscopy (STM) and optical ellipsometry, and have studied the kinetics of film growth. We suggest that self-assembled phenylene ethynylene oligomers on Au(111) surfaces grow as thiols rather than as thiolates. Using low-temperature STM, we collected local current-voltage spectra showing negative differential resistance at 6 K.     

Self-assembly of manganese phthalocyanine on Pb(111) surface: a scanning tunneling microscopy study

The self-assembled structure of submonolayer manganese phthalocyanine (MnPc) on Pb(111) surface is investigated by using low-temperature scanning tunneling microscopy (STM). A "holelike" superlattice, which is superimposed on the self-assembled nearly quadratic network, is observed. High resolution STM images reveal that there are two distinct azimuthal orientations of MnPc molecules. It is found that by taking the two different orientations the self-assembly can further be optimized energetically by maximizing intermolecular orbital overlapping. It is this intralayer energy minimization process that leads to the characteristic holelike superlattice.     

Competitive Metal Coordination of Hexaaminotriphenylene on Cu(111) by Intrinsic Copper Versus Extrinsic Nickel Adatoms

The interplay between the self-assembly and surface chemistry of 2,3,6,7,10,11-hexaaminotriphenylene (HATP) on Cu(111) was complementarily studied by high-resolution scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) under ultra-high vacuum conditions. To shed light on the competitive metal coordination, comparative experiments were carried out on pristine and nickel-covered Cu(111). Directly after room-temperature deposition of HATP onto pristine Cu(111), self-assembled aggregates were observed by STM, and XPS results indicated still protonated amino groups. Annealing up to 200 °C activated the progressive single deprotonation of all amino groups as indicated by chemical shifts of both the N 1s and C 1s core levels in the XP spectra. This enabled the formation of topologically diverse π–d conjugated coordination networks with intrinsic copper adatoms. The basic motif of these networks was a metal–organic trimer, in which three HATP molecules were coordinated by Cu₃ clusters, as corroborated by the accompanying density functional theory (DFT) simulations. Additional deposition of more reactive nickel atoms resulted in both chemical and structural changes with deprotonation and formation of bis(diimino)–Ni bonded networks already at room temperature. Even though fused hexagonal metal-coordinated pores were observed, extended honeycomb networks remained elusive, as tentatively explained by the restricted reversibility of these metal–organic bonds.     

Self-assembly of a Rh(I) complex on Au(111) surfaces and its electrocatalytic activity toward the hydrogen evolution reaction

The self-assembly of a Wilkinson type of catalyst molecule, trans-RhCl(CO)(PPh3)2, on Au(111) surfaces and its electrocatalytic properties toward the hydrogen evolution reaction (HER) are investigated by employing scanning tunneling microscopy (STM), cyclic voltammetry (CV), and X-ray photoelectron spectroscopy (XPS). The self-assembled monolayers of RhCl(CO)(PPh3)2 are prepared from either dichloromethane or aqueous solutions, but the ordered structures are observed only in atmospheric conditions after solvents evaporate. In the electrolyte solutions, disordered yet uniformly sized spherical clusters of individual molecules are observed as a result of the conformational change of the molecule by the solvation effect of water. The immobilized Rh(I) molecular clusters are electrochemically stable in a wide potential window and exhibit remarkable electrocatalytic activity toward HER in perchloric acid solutions. Several comparative experiments involving similar types of immobilized complexes containing Ru(I) and Ir(I) centers and solution species of RhCl(CO)(PPh3)2 are performed. However, none of them are found to be electroactive to HER. The Tafel slope of HER on the Rh(I) complex modified Au(111) electrode in 0.1 M HClO4 is determined to be -0.061 V, which is almost in the middle of those on bare Au(111) (-0.093 V) and Rh covered (thetaRh approximately 0.3) Au(111) (-0.034 V) electrodes. XPS measurements reveal a valence change of Rh(I) to Rh(0), and an oxidative addition and reductive elimination mechanism is suggested for the enhancement of HER.     

Supramolecular assembly of strongly chemisorbed size- and shape-defined chiral clusters: S- and R-alanine on Cu(110)

The bonding and self-assembly of a chirally organized monolayer of alanine on the Cu(110) surface has been investigated using reflection-absorption infrared spectroscopy, low-energy electron diffraction (LEED), and scanning tunneling microscopy (STM). This multitechnique approach has enabled an in-depth understanding of the hierarchy of chirality transfer: from a single adsorbed molecule, to size-defined chiral clusters, and then to an overall chiral assembly. The data have indicated that the alanine is in its anionic form, bound to the copper surface through the oxygens of the ionized carboxylate group and the nitrogen of the neutral amino group. Importantly, the methyl group is held away from the surface, resulting in direct chirality transfer into the footprint of the adsorbed alanine molecules, with the local adsorption motif for S-alanine being the mirror image of that created for R-alanine. STM has shown that S-alanine molecules self-organize to form size-defined chiral clusters of six or eight molecules at the surface, interspersed with chiral channels of bare metal. Together, these clusters and channels further self-assemble into a chiral array with one unique chiral domain sustained across the entire surface. A similar chiral assembly, but with the mirror organization, has been observed for R-alanine. Structural models for the individual clusters are proposed, and in conjunction with LEED data, overall models for these chiral phases of both S- and R-alanine have been constructed. Overall, this adsorption system has been found to be both strongly chemisorbed and capable of extensive intermolecular H-bonding, causing stresses that lead not only to the chiral self-organization of molecules but also to a specific self-organization of the empty chiral channels and spaces that intersperse the structure which, in turn, chirally assemble across macroscopic length scales to give a surface with global organizational chirality.     

Self-assembly of L-tryptophan on Cu(111) studied by low-temperature scanning tunneling microscopy

The self-assembly of L-tryptophan on Cu(111) is investigated by an ultrahigh vacuum scanning tunneling microscope (STM) at 4.4 K. A series of novel supramolecular structures have been prepared with different annealing temperatures.     

Self-assembly of l-tryptophan on Cu(111) studied by low-temperature scanning tunneling microscopy

The self-assembly of l-tryptophan on Cu(111) is investigated by an ultrahigh vacuum scanning tunneling microscope (STM) at 4.4 K. When deposited onto the substrate at around 120 K with a coverage of 0.1 monolayer, molecular trimers, tetramers, hexamers, and chains coexist on Cu(111). Then almost all molecules self-assemble into chiral hexamers after being annealed at room temperature. When increasing molecular coverage to the full layer, a new type of chain is observed on the surface. Based on the high-resolution STM images at sub-molecular level, we suggest that the l-tryptophan molecules are present in neutral, zwitterionic or anionic states in these structures.     

Quantum size effect directed selective self-assembling of cobalt phthalocyanine on Pb(111) thin films

Adsorption and self-assembly of cobalt phthalocyanine (CoPc) molecules on Pb(111) thin films with a thickness ranging from 10 atomic monolayers (ML) to 20 ML were investigated by using scanning tunneling microscopy and spectroscopy (STM/STS). Unprecedented thickness-selective oscillating adsorption and self-assembly behavior of the molecules on the films were observed. STS measurement reveals that this oscillatory behavior arises from quantum size effect. The strong quantum confinement of electron motion in the Pb films modulates the electronic density of states at the Fermi level (DOS(EF)), leading to preferential adsorption at thicknesses of higher DOS(EF). The work provides an unambiguous evidence for quantum modulation of surface reactivities of a metal thin film.     

Design and Self-assembly of a Novel Tetranuclear Zinc(Ⅱ) Complex via Reaction of 1,3-Thiazolidine-2-thione (tzdtH) with Zn(NO3)2

Introduction The self-assembly of clusters in inorganic systems is an interesting subject. The self-assembly of big molecules has been well established in biological systems[1-5].     

Self-Assembled Monolayers of N-Heterocyclic Olefins on Au(111)

Self-assembled monolayers (SAMs) of N-heterocyclic olefins (NHOs) have been prepared on Au(111) and their thermal stability, adsorption geometry, and molecular order were characterized by X-ray photoelectron spectroscopy, polarized X-ray absorption spectroscopy, scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. The strong σ-bond character of NHO anchoring to Au induced high geometrical flexibility that enabled a flat-lying adsorption geometry via coordination to a gold adatom. The flat-lying adsorption geometry was utilized to further increase the surface interaction of the NHO monolayer by backbone functionalization with methyl groups that induced high thermal stability and a large impact on work-function values, which outperformed that of N-heterocyclic carbenes. STM measurements, supported by DFT modeling, identified that the NHOs were self-assembled in dimers, trimers, and tetramers constructed of two, three, and four complexes of NHO−Au-adatom. This self-assembly pattern was correlated to strong NHO−Au interactions and steric hindrance between adsorbates, demonstrating the crucial influence of the carbon-metal σ-bond on monolayer properties.     

Self-assembled monolayer and multilayer films of the nanocluster [HxPMo12O40 subsetH4Mo72Fe30(O2CMe)15O254(H2O)68] on gold

Films of the molybdenum-iron nanocluster [H x PMo 12O 40 subsetH 4Mo 72Fe 30(O 2CMe) 15O 254(H2O) 68] (FeMoC) were generated on gold via the self-assembly technique using two divergent routes. The first route entails the self-assembly of unfunctionalized FeMoC onto a preprepared carboxyl-terminated SAM on gold. The second route involves the preparation of thiol-terminated functionalized FeMoC clusters, which are then allowed to self-assemble onto bare gold surfaces. Monolayer films of FeMoC clusters are attained via both routes, with the second route requiring shorter immersion times (2 days) than the first route (6 days). Multilayer films of FeMoC are formed via the second route for immersion times longer than 2 days. Characterization of these films using optical ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy confirm the self-assembly of the clusters on the surfaces.     

Pinning mass-selected Agn clusters on the TiO2(110)-1x1 surface via deposition at high kinetic energy

We present the first scanning tunneling microscopy (STM) study of the deposition of mass-selected silver clusters (Ag(n),n=1, 2, 3) on a rutile TiO(2)(110)-1x1 surface at room temperature under hard-landing conditions. Under hard-landing conditions, only small features are observed on the surface in all cases without sintering or surface damage. This suggests that the high impact energy of the clusters mainly dissipates as thermal energy in the substrate, resulting in the recovery of any initial impact-induced surface damage and the formation of bound clusters on the surface near the impact point. STM images indicate that Ag(1) binds on the bridging oxygen rows twice as often as on the Ti rows. Density-functional Theory (DFT) calculations are consistent with Ag(1) binding at either bridging oxygen vacancies or with two adjacent bridging oxygen atoms in the same bridging oxygen row. STM images of Ag(2) and Ag(3) depositions indicate almost exclusive binding centered on the Ti-atom rows. DFT calculations suggest that the Ag(2) and Ag(3) clusters are bound between two bridging oxygen rows, which is consistent with the STM observations.     

Assembly of linear clusters of iodobenzene dimers on Cu(110)

Low-temperature STM observations of the low-coverage chemisorption behavior of iodobenzene on Cu(110) are presented at two annealing temperatures. When a random distribution of isolated iodobenzene molecules deposited at T < 100 K is annealed to approximately 170 K, the undissociated molecules assemble into chainlike clusters composed of identical subunits. An STM tip-induced dissociation reaction is used to determine that the individual units in the chains are composed of pairs of iodobenzene molecules. A model is proposed in which iodine atoms on each member of the pair are directed toward one another. The driving force for the formation of such clusters is suggested to be the dispersion interactions between the polarizable iodobenzene molecules.     

Tailoring the Self-assembly of Melamine on Au (111) via Doping with Cu Atoms

The doping effect of Cu on the self-assembly film of melamine on an Au(111) surface has been investigated with scanning tunneling microscopy (STM). The evaporated Cu adatoms occupy the positions underneath the amino groups and change the hydrogen bonding pattern between the melamine molecules. Accordingly, the self-assembly structure has changed stepwise from a well-defined honeycomb into a track-like and then a triangular structure depending on the amount of Cu adatoms. The interaction between Cu adatom and melamine is moderate thus the Cu adatoms can be released upon mild heating to around 100℃. These findings are different from previous observations of either the coordination assembly or the physically trapped metal adatoms.     

Simulation of metal-ligand self-assembly into spherical complex m(6)l(8)

Molecular dynamics simulations were performed to study the self-assembly of a spherical complex through metal-ligand coordination interactions. M(6)L(8), a nanosphere with six palladium ions and eight pyridine-capped tridentate ligands, was selected as a target system. We successfully observed the spontaneous formation of spherical shaped M(6)L(8) cages over the course of our simulations, starting from random initial placement of the metals and ligands. To simulate spontaneous coordination bond formations and breaks, the cationic dummy atom method was employed to model nonbonded metal-ligand interactions. A coarse-grained solvent model was used to fill the gap between the time scale of the supramolecular self-assembly and that accessible by common molecular dynamics simulation. The simulated formation process occurred in the distinct three-stage (assembly, evolution, fixation) process that is well correlated with the experimental results. We found that the difference of the lifetime (or the ligand exchange rate) between the smaller-sized incomplete clusters and the completed M(6)L(8) nanospheres is crucially important in their supramolecular self-assembly.     

C-H...F hydrogen bonding: the origin of the self-assemblies of bis(2,2'-difluoro-1,3,2-dioxaborine)

The effect of the molecular structure on the self-assembly of specially designed two-core 1,3,2-dioxaborines has been studied with various techniques. It was found that the molecules spontaneously adsorbed on HOPG surfaces and self-organized into well-ordered two-dimensional (2D) monolayers. The structural details of the 2D assemblies were investigated by scanning tunneling microscopy (STM). From X-ray analysis of the corresponding three-dimensional (3D) crystal and from theoretical calculation, we were able to reveal the driving force behind the specific self-assembly. The C-H...F hydrogen bonding between the ortho carbon of the phenyl ring and the fluorine of the BF2 group plays an important role in the formation of the adlayers. The different electron affinities and geometries of the molecules affect the intermolecular interactions which further lead to different properties in the bulk materials.     

Encapsulated Pd nanocrystals supported by nanoline-structured SrTiO3(001)

Palladium nanocrystals were grown on a nanostructured SrTiO(3)(001) surface and annealed in ultrahigh vacuum at 620 degrees C. This leads to the so-called strong metal-support interaction (SMSI) state, characterized by encapsulation of the metal clusters with an oxide layer. Scanning tunneling microscopy (STM) of the oxide adlayer on the Pd(111) cluster surface reveals two superstructures with different lattice parameters and crystallographic rotations. Interpretation of the STM images is most readily achieved via noncommensurate TiO(x)() surface layers which result in two distinct Moiré patterns.     

Scanning tunneling microscopy studies of metal clusters supported on TiO2 (110): Morphology and electronic structure

A brief review of our laboratory's recent scanning tunneling microscopy (STM) studies on nanoclusters supported on TiO₂(110) is presented. Particular emphasis is placed on the system Au/TiO₂(110). The nucleation and growth of the clusters, which were vapor-deposited on TiO₂(110) under ultra high vacuum (UHV) conditions, were investigated using STM. It was found that Au, Pd, and Ag clusters all grow in a three-dimensional (3D) (Volmer-Weber) fashion on TiO₂(110), but that at low coverages, quasi-two dimensional (quasi-2D) Au and Pd clusters were observed. These quasi-2D clusters are characterized by heights of 1–2 atomic layers. Annealing studies show that Au and Pd clusters form large microcrystals with well-defined hexagonal shapes. Al clusters, which have a strong interaction with the substrate, are oxidized upon deposition, “wetting” the surface and forming small clusters. In addition to the topographic studies, the local electronic properties of these clusters have been studied using scanning tunneling spectroscopy (STS) to measure the cluster band gaps. The electronic structure was found to be cluster size-dependent, as seen by the appearance of a band gap as the cluster size decreased. More specifically, the onset of cluster metallic properties correlates with the transition from quasi-2D to 3D cluster growth.     

Hierarchical self-assembly of designed 2 x 2-alpha-helix bundle proteins on Au(111) surfaces

Self-assembled monolayers of biomolecules on atomically planar surfaces offer the prospect of complex combinations of controlled properties, e.g., for bioelectronics. We have prepared a novel hemi-4-alpha-helix bundle protein by attaching two alpha-helical peptides to a cyclo-dithiothreitol (cyclo-DTT) template. The protein was de novo designed to self-assemble in solution to form a 4-alpha-helix bundle, whereas the disulfide moiety enables the formation of a self-assembled monolayer on a Au(111) surface by opening of the disulfide, thus giving rise to a two-step self-assembly process. The 2 x 2-alpha-helix bundle protein and its template were studied by X-ray photo electron spectroscopy (XPS), electrochemical methods, and electrochemical in situ scanning tunneling microscopy (in situ STM). XPS showed that the cyclo-DTT opens on adsorption to a gold surface with the integrity of the 2 x 2-alpha-helix bundle proteins retained. The surface properties of the DTT and 2 x 2-alpha-helix bundle protein adlayer were characterized by interfacial capacitance and impedance techniques. Reductive desorption was used to determine the coverage of the adlayers, giving values of 65 and 16 muC cm(-2) for DTT and 2 x 2-helix, respectively. The 2 x 2-alpha-helix bundle protein adlayers were imaged by in situ STM. The images indicated a dense monolayer according with the voltammetric data. No long-range order could be detected, but two clearly distinct STM contrasts were assigned to 2 x 2-alpha-helix bundle protein molecules oriented in parallel and antiparallel conformations. The template molecule DTT alone forms highly ordered 30-40 nm domains, giving an adlayer density which agreed well with the coverage determined by voltammetry. This could be exploited in STM imaging of mixed DTT/2 x 2-alpha-helix bundle protein monolayers, with clearly distinct STM patterns of the two components.     

Graphene功能分子在HOPG上自组装结构的密度泛函研究

Graphene自组装超分子结构,是指FTBC-Cn(n=4,6,8,12)分子有序自组装在高定向裂解石墨(HOPG)上形成的自组装超分子结构,是一种新型二维固体表面材料.其中FTBC-Cn分子是由三角形扶手椅型graphene每边添加2条含有n(n=4,6,8,12)个C原子的烷基链所形成具有曲面结构的一种分子.采用...