Initial coupling and reaction progression of directly deposited biradical graphene nanoribbon monomers on iodine-passivated versus pristine Ag(111)

The development of widely applicable methods for the synthesis of C-C-bonded nanostructures on inert and insulating surfaces is a challenging yet rewarding milestone in the field of on-surface synthesis. This would enable studies of nearly unperturbed covalent nanostructures with unique electronic properties as graphene nanoribbons (GNR) and π-conjugated 2D polymers. The prevalent Ullmann-type couplings are almost exclusively carried out on metal surfaces to lower the temperature required for initial dehalogenation well below the desorption threshold. To overcome the necessity for the activation of monomers on the target surface, we employ a recently developed Radical Deposition Source (RaDeS) for the direct deposition of radicals onto inert surfaces for subsequent coupling by addition reactions. The radicals are generated en route by indirect deposition of halogenated precursors through a heated reactive tube, where the dehalogenation reaction proceeds. Here, we use the ditopic 6,11-diiodo-1,2,3,4-tetraphenyltriphenylene (DITTP) precursor that afforded chevron-like GNR on Au(111) via the usual two-staged reaction comprised of monomer-coupling into covalent polymers and subsequent formation of an extended GNR by intramolecular cyclodehydrogenation (CDH). As a model system for inert surfaces, we use Ag(111) passivated with a closed monolayer of chemisorbed iodine that behaves in an inert manner with respect to dehalogenation reactions and facilitates the progressive coupling of radicals into extended covalent structures. We deposit the DITTP-derived biradicals onto both iodine-passivated and pristine Ag(111) surfaces. While on the passivated surface, we directly observe the formation of covalent polymers, on pristine Ag(111) organometallic intermediates emerge instead. This has decisive consequences for the further progression of the reaction: heating the organometallic chain directly on Ag(111) results in complete desorption, whereas the covalent polymer on iodine-passivated Ag(111) can be transformed into the GNR. Yet, the respective CDH proceeds directly on Ag(111) after thermal desorption of the iodine passivation. Accordingly, future work is aimed at the further development of approaches for the complete synthesis of GNR on inert surfaces

Competitive metal‐coordination of hexaaminotriphenylene on Cu(111) by intrinsic copper versus extrinsic nickel adatoms

The interplay between self‐assembly and surface chemistry of 2,3,6,7,10,11‐hexaminotriphenylene (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 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, while XPS indicated non‐deprotonated amino groups. Annealing up to 200 °C activated the progressive single deprotonation of all amino groups as indicated by chemical shifts of both N 1s and C 1s core levels in the XP spectra. This enabled the formation of topologically versatile π‐d conjugated coordination networks with intrinsic copper adatoms. The basic motif of these networks was a metal‐organic trimer, where three HATP molecules were coordinated by Cu3 clusters, as corroborated by 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 pores were observed, extended honeycomb networks remained elusive, as tentatively explained by a restricted reversibility of these metal‐organic bonds

Self-assembly of melem on Ag(111)—emergence of porous structures based on amino-heptazine hydrogen bonds

Self-assembly of melem on Ag(111) as studied by Scanning-Tunneling-Microscopy (STM) in ultra-high vacuum revealed a great structural variety. In total, five porous and two densely packed monolayer polymorphs were observed. All structures are stabilized by intermolecular hydrogen bonds, where melem–melem arrangements are based on very few basic motifs. Six out of seven polymorphs can be described by a unified concept

Thermodynamics of 4,4 '-stilbenedicarboxylic acid monolayer self-assembly at the nonanoic acid-graphite interface

A direct calorimetric measurement of the overall enthalpy change associated with self-assembly of organic monolayers at the liquid–solid interface is for most systems of interest practically impossible. In previous work we proposed an adapted Born–Haber cycle for an indirect assessment of the overall enthalpy change by using terephthalic acid monolayers at the nonanoic acid–graphite interface as a model system. To this end, the sublimation enthalpy, dissolution enthalpy, the monolayer binding enthalpy in vacuum, and a dewetting enthalpy are combined to yield the total enthalpy change. In the present study the Born–Haber cycle is applied to 4,40 -stilbenedicarboxylic acid monolayers. A detailed comparison of these two aromatic dicarboxylic acids is used to evaluate and quantify the contribution of the organic backbone for stabilization of the monolayer at the nonanoic acid–graphite interface

From Au-Thiolate Chains to Thioether Sierpiński Triangles: The Versatile Surface Chemistry of 1,3,5-Tris(4-Mercaptophenyl)Benzene on Au(111)

Self-assembly of 1,3,5-tris(4-mercaptophenyl)benzene (TMB) – a three-fold symmetric, thiol functionalized aromatic molecule – was studied on Au(111) with the aim to realize extended Au-thiolate linked molecular architectures. The focus lay on resolving thermally activated structural and chemical changes by a combination of microscopy and spectroscopy. Thereby Scanning Tunneling Microscopy provided submolecularly resolved structural information, while the chemical state of sulfur was assessed by X-ray Photoelectron Spectroscopy. Directly after room temperature deposition only less well ordered structures were observed. Mild annealing promoted the first structural transition into ordered molecular chains, partly organized in homochiral molecular braids. Further annealing led to self-similar Sierpiński triangles, while annealing at even higher temperatures again resulted in mostly disordered structures. Both the irregular aggregates observed at room temperature and the chains were identified as metal-organic assemblies, whereby two out of the three intermolecular binding motifs are energetically equivalent according to Density Functional Theory simulations. The emergence of Sierpiński triangles is driven by a chemical transformation, i.e. the conversion of coordinative Au-thiolate to covalent thioether linkages, and can be further understood by Monte Carlo simulations. The great structural variance of TMB on Au(111) can on one hand be explained by the energetic equivalence of two binding motifs. On the other hand, the unexpected chemical transition even enhances the structural variance and results in thiol-derived covalent molecular architectures

Quantifying the ultraslow desorption kinetics of 2,6-naphthalenedicarboxylic acid monolayers at liquid–solid interfaces

Kinetic effects in monolayer self-assembly at liquid–solid interfaces are not well explored but can provide unique insights. We use variable-temperature scanning tunneling microscopy (STM) to quantify the desorption kinetics of 2,6-naphthalenedicarboxylic acid (NDA) monolayers at nonanoic acid–graphite interfaces. Quantitative tracking of the decline of molecular coverages by STM between 57.5 and 65.0 °C unveiled single-exponential decays over the course of days. An Arrhenius plot of rate constants derived from fits results in a surprisingly high energy barrier of 208 kJ mol–1 that strongly contrasts with the desorption energy of 16.4 kJ mol–1 with respect to solution as determined from a Born–Haber cycle. This vast discrepancy indicates a high-energy transition state. Expanding these studies to further systems is the key to pinpointing the molecular origin of the remarkably large NDA desorption barrier

Mechanistic insights into on-surface reactions from isothermal temperature-programmed X-ray photoelectron spectroscopy

On-surface synthesis often proceeds under kinetic control due to the irreversibility of key reaction steps, rendering kinetic studies pivotal. The accurate quantification of reaction rates also bears potential for unveiling reaction mechanisms. Temperature-Programmed X-ray Photoelectron Spectroscopy (TP-XPS) has emerged as an analytical tool for kinetic studies with splendid chemical and sufficient temporal resolution. Here, we demonstrate that the common linear temperature ramps lead to fitting ambiguities. Moreover, pinpointing the reaction order remains intricate, although this key parameter entails information on atomistic mechanisms. Yet, TP-XPS experiments with a stepped temperature profile comprised of isothermal segments facilitate the direct quantification of rate constants from fitting time courses. Thereby, rate constants are obtained for a series of temperatures, which allows independent extraction of both activation energies and pre-exponentials from Arrhenius plots. By using two analogous doubly versus triply brominated aromatic model compounds, we found that their debromination on Ag(111) is best modeled by second-order kinetics and thus proceeds via the involvement of a second, non-obvious reactant. Accordingly, we propose that debromination is activated by surface supplied Ag adatoms. This hypothesis is supported by Density Functional Theory (DFT) calculations. We foresee auspicious prospects for this TP-XPS variant for further exploring the kinetics and mechanisms of on-surface reactions

Origin of solvent-induced polymorphism in self-assembly of trimesic acid monolayers at solid-liquid interfaces

Encoding information in the chemical structure of tectons is the pivotal strategy in self-assembly for the realization of targeted supramolecular structures. However, frequently observed polymorphism in supramolecular monolayers provides experimental evidence for a decisive additional influence of environmental parameters, such as solute concentration or type of solvent, on structure selection. While concentration-induced polymorphism is comparatively well understood, the thermodynamical and molecular origins of solvent-induced polymorphism remain elusive. To shed light on this fundamental aspect of self-assembly, we explore the solvent-induced polymorphism of trimesic acid (TMA) monolayers on graphite as prototypical example. Using the homologous series of fatty acids as solvents, TMA self-assembles into the anticipated chickenwire polymorph for longer chain fatty acids, whereas the more densely packed, but still porous flower polymorph emerges in shorter chain fatty acids. According to our initial working hypothesis, the origin of this solvent-induced polymorphism lies in a solvent-dependence of the free energy gain. Utilizing an adapted Born-Haber cycle constructed from measured TMA sublimation and dissolution enthalpies as well as Density Functional Theory calculated monolayer binding energies, we quantitatively assessed the self-assembly thermodynamics of both polymorphs in hexanoic, heptanoic, and nonanoic acid. Yet, in contrast to the experimental findings, these results suggest superior thermodynamical stability of the chickenwire polymorph in all solvents. On the other hand, additional experiments comprising variable temperature Scanning Tunneling Microscopy corroborate that the flower polymorph is thermodynamically most stable in hexanoic acid. To resolve this apparent contradiction, we propose a thermodynamical stabilization of the flower polymorph in hexanoic acid through the stereochemically specific co-adsorption of shape-matched solvent molecules in its unique smaller elongated pores. This alternative explanation gains further support from experiments with side-substituted hexanoic acid solvents. Combination of a quantitative thermodynamic analysis and studies with systematic variations of the solvent’s molecular structure holds great promise to enhance the understanding of thus far underexplored solvent effects

What can be inferred from moiré patterns? A case study of trimesic acid monolayers on graphite

Self-assembly of benzene-1,3,5-tricarboxylic acid (trimesic acid - TMA) monolayers at the alkanoic acid-graphite interface is revisited. Even though this archetypal model system for hydrogen bonded porous networks is particularly well studied, the analysis of routinely observed superperiodic contrast modulations known as moiré patterns lags significantly behind. Fundamental questions remain unanswered: Are moiré periodicity and orientation always the same, i.e. is exclusively only one specific moiré pattern observed? What are the geometric relations (superstructure matrices) between moiré, TMA, and graphite lattices? What affects the moiré pattern formation? Is there any influence of solvent, conentration, or thermal treatment? These basic questions are addressed by Scanning Tunneling Microscopy experiments at the liquid-solid interface, revealing a variety of different moiré patterns. Interestingly, TMA and graphite lattices were always found to be ~5° rotated with respect to each other. Consequently, the observed variation in moiré patterns is attributed to minute deviations (<2°) from this preferred orientation. Quantitaive analysis of moiré periods and orientations facilitates determination of the TMA lattice parameter with picometer precsion