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.

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.

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.

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.

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.

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.

Bifunctional DNA architectonics: three-way junctions with sticky perylene bisimide caps and a central metal lock.

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.

Energy transfer between eigenmodes in multimodal atomic force microscopy.

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.

Amplitude modulation dynamic force microscopy imaging in liquids with atomic resolution: comparison of phase contrasts in single and dual mode operation.

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.

Biosupramolecular nanowires from chlorophyll dyes with exceptional charge-transport properties.

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.

Chemical bond imaging using torsional and flexural higher eigenmodes of qPlus sensors.

Non-contact atomic force microscopy (AFM) with CO-functionalized tips allows visualization of the chemical structure of adsorbed molecules and identify individual inter- and intramolecular bonds. This technique enables in-depth studies of on-surface reactions and self-assembly processes. Herein, we analyze the suitability of qPlus sensors, which are commonly used for such studies, for the application of modern multifrequency AFM techniques. Two different qPlus sensors were tested for submolecular resolution imaging via actuating torsional and flexural higher eigenmodes and via bimodal AFM. The torsional eigenmode of one of our sensors is perfectly suited for performing lateral force microscopy (LFM) with single bond resolution. The obtained LFM images agree well with images from the literature, which were scanned with customized qPlus sensors that were specifically designed for LFM. The advantage of using a torsional eigenmode is that the same molecule can be imaged either with a vertically or laterally oscillating tip without replacing the sensor simply by actuating a different eigenmode. Submolecular resolution is also achieved by actuating the 2nd flexural eigenmode of our second sensor. In this case, we observe particular contrast features that only appear in the AFM images of the 2nd flexural eigenmode but not for the fundamental eigenmode. With complementary laser Doppler vibrometry measurements and AFM simulations we can rationalize that these contrast features are caused by a diagonal (i.e. in-phase vertical and lateral) oscillation of the AFM tip.

Topological Stone-Wales Defects Enhance Bonding and Electronic Coupling at the Graphene/Metal Interface.

Defects play a critical role for the functionality and performance of materials, but the understanding of the related effects is often lacking, because the typically low concentrations of defects make them difficult to study. A prominent case is the topological defects in two-dimensional materials such as graphene. The performance of graphene-based (opto-)electronic devices depends critically on the properties of the graphene/metal interfaces at the contacting electrodes. The question of how these interface properties depend on the ubiquitous topological defects in graphene is of high practical relevance, but could not be answered so far. Here, we focus on the prototypical Stone-Wales (S-W) topological defect and combine theoretical analysis with experimental investigations of molecular model systems. We show that the embedded defects undergo enhanced bonding and electron transfer with a copper surface, compared to regular graphene. These findings are experimentally corroborated using molecular models, where azupyrene mimics the S-W defect, while its isomer pyrene represents the ideal graphene structure. Experimental interaction energies, electronic-structure analysis, and adsorption distance differences confirm the defect-controlled bonding quantitatively. Our study reveals the important role of defects for the electronic coupling at graphene/metal interfaces and suggests that topological defect engineering can be used for performance control.

Electrostatic interaction forces in aqueous salt solutions of variable concentration and valency.

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.

Constructing covalent organic nanoarchitectures molecule by molecule via scanning probe manipulation.

Constructing low-dimensional covalent assemblies with tailored size and connectivity is challenging yet often key for applications in molecular electronics where optical and electronic properties of the quantum materials are highly structure dependent. We present a versatile approach for building such structures block by block on bilayer sodium chloride (NaCl) films on Cu(111) with the tip of an atomic force microscope, while tracking the structural changes with single-bond resolution. Covalent homo-dimers in cis and trans configurations and homo-/hetero-trimers were selectively synthesized by a sequence of dehalogenation, translational manipulation and intermolecular coupling of halogenated precursors. Further demonstrations of structural build-up include complex bonding motifs, like carbon-iodine-carbon bonds and fused carbon pentagons. This work paves the way for synthesizing elusive covalent nanoarchitectures, studying structural modifications and revealing pathways of intermolecular reactions.

Surface-controlled reversal of the selectivity of halogen bonds.

Intermolecular halogen bonds are ideally suited for designing new molecular assemblies because of their strong directionality and the possibility of tuning the interactions by using different types of halogens or molecular moieties. Due to these unique properties of the halogen bonds, numerous areas of application have recently been identified and are still emerging. Here, we present an approach for controlling the 2D self-assembly process of organic molecules by adsorption to reactive vs. inert metal surfaces. Therewith, the order of halogen bond strengths that is known from gas phase or liquids can be reversed. Our approach relies on adjusting the molecular charge distribution, i.e., the σ-hole, by molecule-substrate interactions. The polarizability of the halogen and the reactiveness of the metal substrate are serving as control parameters. Our results establish the surface as a control knob for tuning molecular assemblies by reversing the selectivity of bonding sites, which is interesting for future applications.