Deciphering the Mechanism of On-Surface Dehydrogenative C-C Coupling Reactions.

On-surface synthesis has proven to be a powerful approach for fabricating various low-dimensional covalent nanostructures with atomic precision that could be challenging for conventional solution chemistry. Dehydrogenative Caryl-Caryl coupling is one of the most popular on-surface reactions, of which the mechanisms, however, have not been well understood due to the lack of microscopic insights into the intermediates that are fleetingly existing under harsh reaction conditions. Here, we bypass the most energy-demanding initiation step to generate and capture some of the intermediates at room temperature (RT) via the cyclodehydrobromination of 1-bromo-8-phenylnaphthalene on a Cu(111) surface. Bond-level scanning probe imaging and manipulation in combination with DFT calculations allow for the identification of chemisorbed radicals, cyclized intermediates, and dehydrogenated products. These intermediates correspond to three main reaction steps, namely, debromination, cyclization (radical addition), and H elimination. H elimination is the rate-determining step as evidenced by the predominant cyclized intermediates. Furthermore, we reveal a long-overlooked pathway of dehydrogenation, namely, atomic hydrogen-catalyzed H shift and elimination, based on the observation of intermediates for H shift and superhydrogenation and the proof of a self-amplifying effect of the reaction. This pathway is further corroborated by comprehensive theoretical analysis on the reaction thermodynamics and kinetics.

Imaging the adsorption sites of organic molecules on metallic surfaces by an adaptive tunnelling current feedback.

Atomic force microscopy (AFM) allows submolecular resolution imaging of organic molecules deposited on a surface by using CO-functionalized qPlus sensors under ultrahigh vacuum and low temperature conditions. However, the experimental determination of the adsorption sites of these organic molecules requires the precise identification of the atomic structure of the surface on which they are adsorbed. Here, we develop an automation method for AFM imaging that provides in a single image both, submolecular resolution on organic molecules and atomic resolution on the surrounding metallic surface. The method is based on an adaptive tunnelling current feedback system that is regulated according to the response of the AFM observables, which guarantees that both the molecules and the surface atoms are imaged under optimum conditions. Therewith, the approach is suitable for imaging adsorption sites of several adjacent and highly mobile molecules such as 2-iodotriphenylene on Ag(111) in a single scan. The proposed method with the adaptive feedback system facilitates statistical analysis of molecular adsorption geometries and could in the future contribute to autonomous AFM imaging as it adapts the feedback parameters depending on the sample properties.

Effect of Amorphous-Crystalline Phase Transition on Superlubric Sliding.

Structural superlubricity describes the state of greatly reduced friction between incommensurate atomically flat surfaces. Theory predicts that, in the superlubric state, the remaining friction sensitively depends on the exact structural configuration. In particular the friction of amorphous and crystalline structures for, otherwise, identical interfaces should be markedly different. Here, we measure friction of antimony nanoparticles on graphite as a function of temperature between 300 and 750 K. We observe a characteristic change of friction when passing the amorphous-crystalline phase transition above 420 K, which shows irreversibility upon cooling. The friction data is modeled with a combination of an area scaling law and a Prandtl-Tomlinson type temperature activation. We find that the characteristic scaling factor γ, which is a fingerprint of the structural state of the interface, is reduced by 20% when passing the phase transition. This validates the concept that structural superlubricity is determined by the effectiveness of atomic force canceling processes.

On-Surface Synthesis and Real-Space Visualization of Aromatic P3 N3.

On-surface synthesis is at the verge of emerging as the method of choice for the generation and visualization of unstable or unconventional molecules, which could not be obtained via traditional synthetic methods. A case in point is the on-surface synthesis of the structurally elusive cyclotriphosphazene (P3 N3 ), an inorganic aromatic analogue of benzene. Here, we report the preparation of this fleetingly existing species on Cu(111) and Au(111) surfaces at 5.2 K through molecular manipulation with unprecedented precision, i.e., voltage pulse-induced sextuple dechlorination of an ultra-small (about 6 Å) hexachlorophosphazene P3 N3 Cl6 precursor by the tip of a scanning probe microscope. Real-space atomic-level imaging of cyclotriphosphazene reveals its planar D3h -symmetric ring structure. Furthermore, this demasking strategy has been expanded to generate cyclotriphosphazene from a hexaazide precursor P3 N21 via a different stimulation method (photolysis) for complementary measurements by matrix isolation infrared and ultraviolet spectroscopy.

Substrate-Modulated Synthesis of Metal-Organic Hybrids by Tunable Multiple Aryl-Metal Bonds.

Assembly of semiconducting organic molecules with multiple aryl-metal covalent bonds into stable one- and two-dimensional (1D and 2D) metal-organic frameworks represents a promising route to the integration of single-molecule electronics in terms of structural robustness and charge transport efficiency. Although various metastable organometallic frameworks have been constructed by the extensive use of single aryl-metal bonds, it remains a great challenge to embed multiple aryl-metal bonds into these structures due to inadequate knowledge of harnessing such complex bonding motifs. Here, we demonstrate the substrate-modulated synthesis of 1D and 2D metal-organic hybrids (MOHs) with the organic building blocks (perylene) interlinked solely with multiple aryl-metal bonds via the stepwise thermal dehalogenation of 3,4,9,10-tetrabromo-1,6,7,12-tetrachloroperylene and subsequent metal-organic connection on metal surfaces. More importantly, the conversion from 1D to 2D MOHs is completely impeded on Au(111) but dominant on Ag(111). We comprehensively study the distinct reaction pathways on the two surfaces by visually tracking the structural evolution of the MOHs with high-resolution scanning tunneling and noncontact atomic force microscopy, supported by first-principles density functional theory calculations. The substrate-dependent structural control of the MOHs is attributed to the variation of the M-X (M = Au, Ag; X = C, Cl) bond strength regulated by the nature of the metal species.

Experimental analysis of tip vibrations at higher eigenmodes of QPlus sensors for atomic force microscopy.

QPlus sensors are non-contact atomic force microscope probes constructed from a quartz tuning fork and a tungsten wire with an electrochemically etched tip. These probes are self-sensing and offer an atomic-scale spatial resolution. Therefore, qPlus sensors are routinely used to visualize the chemical structure of adsorbed organic molecules via the so-called bond imaging technique. This is achieved by functionalizing the AFM tip with a single CO molecule and exciting the sensor at the first vertical cantilever resonance mode. Recent work using higher-order resonance modes has also resolved the chemical structure of single organic molecules. However, in these experiments, the image contrast can differ significantly from the conventional bond imaging contrast, which was suspected to be caused by unknown vibrations of the tip. This work investigates the source of these artefacts by using a combination of mechanical simulation and laser vibrometry to characterize a range of sensors with different tip wire geometries. The results show that increased tip mass and length cause increased torsional rotation of the tuning fork beam due to the off-center mounting of the tip wire, and increased flexural vibration of the tip. These undesirable motions cause lateral deflection of the probe tip as it approaches the sample, which is rationalized to be the cause of the different image contrast. The results also provide a guide for future probe development to reduce these issues.

Thermal Activation of Nanoscale Wear.

Nanoscale wear tracks on ionic crystals are created by reciprocating single asperity scratch tests using atomic force microscopy. The wear characteristics are analyzed by the scratch depth as a function of surface temperature from 25 to 300 K. The average wear depth shows a nonmonotonic behavior as a function of temperature, with a transition between two different regimes characterized by the occurrence of quasiperiodic ripple formation. A thermally activated bond breaking model quantitatively explains the wear data in the low temperature, nonripple regime, but fails above the temperature threshold. This discrepancy is resolved with a geometric separation of the ripple mounds from the troughs, leading to full agreement with Arrhenius kinetics over the full temperature range.

On-Surface Synthesis and Characterization of a Cycloarene: C108 Graphene Ring.

The synthesis of cycloarenes in solution is challenging because of their low solubility and the often hindered cyclodehydrogenation reaction of their nonplanar precursors. Using an alternative on-surface synthesis protocol, we achieved an unprecedented double-stranded hexagonal cycloarene containing 108 sp2 carbon atoms. Its synthesis is based on hierarchical Ullmann coupling and cyclodehydrogenation of a specially designed precursor on a Au(111) surface. The structure and other properties of the cycloarene are investigated by scanning tunneling microscopy/spectroscopy, atomic force microscopy, and density functional theory calculations.

Nanoribbons with Nonalternant Topology from Fusion of Polyazulene: Carbon Allotropes beyond Graphene.

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.

Benzo-Fused Periacenes or Double Helicenes? Different Cyclodehydrogenation Pathways on Surface and in Solution.

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.

Bond-Level Imaging of the 3D Conformation of Adsorbed Organic Molecules Using Atomic Force Microscopy with Simultaneous Tunneling Feedback.

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.

Precise Monoselective Aromatic C-H Bond Activation by Chemisorption of Meta-Aryne on a Metal Surface.

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.

Hierarchical Dehydrogenation Reactions on a Copper Surface.

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.

Friction fluctuations of gold nanoparticles in the superlubric regime.

Superlubricity, or alternatively termed structural (super)lubrictiy, is a concept where ultra-low friction is expected at the interface between sliding surfaces if these surfaces are incommensurate and thus unable to interlock. In this work, we now report on sudden, reversible, friction changes that have been observed during AFM-based nanomanipulation experiments of gold nanoparticles sliding on highly oriented pyrolythic graphite. These effects can be explained by rotations of the gold nanoparticles within the concept of structural superlubricity, where the occurrence of ultra-low friction can depend extremely sensitively on the relative orientation between the slider and the substrate. From our theoretical simulations it will become apparent how even miniscule magnitudes of rotation are compatible to the observed effects and how size and shape of the particles can influence the dependence between friction and relative orientation.

Time Strengthening of Crystal Nanocontacts.

We demonstrate how an exponentially saturating increase of the contact area between a nanoasperity and a crystal surface, occurring on time scales governed by the Arrhenius equation, is consistent with measurements of the static friction and lateral contact stiffness on a model alkali-halide surface at different temperatures in ultrahigh vacuum. The "contact ageing" effect is attributed to atomic attrition and is eventually broken by thermally activated slip of the nanoasperity on the surface. The combination of the two effects also leads to regions of strengthening and weakening in the velocity dependence of the friction, which are well-reproduced by an extended version of the Prandtl-Tomlinson model.

Nanotribological Properties of Hexadecanethiol Self-Assembled Monolayers on Au(111): Structure, Temperature, and Velocity.

Self-assembled monolayers (SAM) are promising building blocks for the optimization of a large variety of systems both on the nano- and on the microscale. Among other applications, SAM are often used as protective coating or friction modifiers. In this work, we have used hexadecanethiol SAM on Au(111) as a model system and studied the different mechanisms of energy dissipation during temperature and velocity dependent friction force microscopy (FFM). In a number of cases, the SAM remained stable during atomic force microscopy experiments and friction-velocity isotherms related dissipation to an activation energy. In other cases, friction experiments lead to an irreversible deterioration of the SAM. This can rather be associated with the general SAM structure that was analyzed by scanning tunneling microscopy and showed a large variety of potential breakdown points like, for example, grain boundaries, step edges, or substrate-related holes in the SAM.

Universal Aging Mechanism for Static and Sliding Friction of Metallic Nanoparticles.

The term "contact aging" refers to the temporal evolution of the interface between a slider and a substrate usually resulting in increasing friction with time. Current phenomenological models for multiasperity contacts anticipate that such aging is not only the driving force behind the transition from static to sliding friction, but at the same time influences the general dynamics of the sliding friction process. To correlate static and sliding friction on the nanoscale, we show experimental evidence of stick-slip friction for nanoparticles sliding on graphite over a wide dynamic range. We can assign defined periods of aging to the stick phases of the particles, which agree with simulations explicitly including contact aging. Additional slide-hold-slide experiments for the same system allow linking the sliding friction results to static friction measurements, where both friction mechanisms can be universally described by a common aging formalism.

ß-Relaxation of PMMA: Tip Size and Stress Effects in Friction Force Microscopy.

The kinetic signature of the ß-relaxation of poly(methyl methacrylate) (PMMA) is investigated by friction force microscopy. The variation in friction force was measured as a function of scan velocity, temperature (300 K-410 K), and applied load using both sharp and blunt probe tips. The friction data show distinct maxima, which can be ascribed to the ß-relaxation of PMMA. The contact area was varied over the ranges of approximately 20 to 70 nm(2) and 12,000 to 43,000 nm(2) through the use of probe tips with radii of approximately 15, 18, 1350, and 2650 nm. Kinetic analysis shows that the apparent activation energy of the ß-relaxation decreases with the tip radius. Accompanying finite element simulations indicate that for the sharp tips a substantial subvolume of the polymer underneath the tip exceeds the yield stress of PMMA. This suggests that for small contact sizes and high stresses the activation barrier of the ß-process decreases through the activation of the α-process by material yielding.

Influence of contact aging on nanoparticle friction kinetics.

One of the oldest concepts in tribology is stick-slip dynamics, where a disruptive sequence of stick and slip phases determine the overall resistance in sliding friction. While the mechanical energy dissipates in the sudden slip phase, the stick phase has been shown to be characterized by contact strengthening mechanisms, also termed contact aging. We present experiments of sliding nanoparticles, where friction is measured as a function of sliding velocity and interface temperature. The resulting complex interdependence is in good agreement with Monte Carlo simulations, in which the energy barrier for contact breaking increases logarithmically with time, at a rate governed by thermal activation.

Frictional dissipation in a polymer bilayer system.

Sliding friction between a silicon tip and a polymer bilayer system consisting of a polystyrene (PS) film covered with a few-nanometers-thick capping layer of hard plasma polymer is studied using friction force microscopy. The system was chosen to enable subsurface dissipation channels to be distinguished from surface friction. Frictional energy dissipation in the underlayer can be identified through the kinetics of the polymer relaxation modes that we measured using nanoscale friction experiments as a function of sample temperature, scanning velocity, and applied load. We found a strong nonlinear increase in friction as a function of applied load around the glass-transition temperature of the PS underlayer. This behavior is a clear signature of frictional dissipation occurring in the volume of the polystyrene layer, well below the surface of the sample. The time-temperature kinetics associated with frictional energy dissipation into the PS was found to be in agreement with the known material properties of PS. Moreover, the data was found to support the hypothesis that the observed friction can be understood as the sum of friction resulting from the relaxation process in the polymer underlayer induced by stress due to the sliding of the tip and a second term associated with dissipation due to sliding friction on the capping layer.