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

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

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

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

Thermodynamics of halogen bonded monolayer self-assembly at the liquid-solid interface

Monolayer self-assembly of a hexabrominated, three-fold symmetric aromatic molecule is studied at the heptanoic acid-graphite interface. Thermodynamical insights are obtained from an adapted Born-Haber cycle that is utilized to derive the overall enthalpy change including solvent effects. Comparison with theoretical entropy estimates suggests a minor influence of solvation

Laser-Bio-Dynamik. Grundlagen zur lasergestuetzten Erfassung von Bioparametern im Pico- bis Attoliterbereich. Teilprojekt: Grundlagenuntersuchungen zur Photo- und mechanischen Nanomanipulation biologischen Materials fuer die medizinische Diagnostik Abschlussbericht

Available from TIB Hannover: F04B186 / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekSIGLEBundesministerium fuer Bildung und Forschung (BMBF), Bonn (Germany)DEGerman