Molecular self-assembly at nanometer scale modulated surfaces: trimesic acid on Ag(111), Cu(111) and Ag/Cu(111)

Baviloliaei, Mahdi Sadeghzadeh; Diekhöner, Lars

doi:10.1039/c4cp01429d

Cited by 23 publications

(34 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Hence, they can be considered as an ex situ heating method. On the other hand, for the ultrahigh vacuum (UHV) conditions, while the temperature at which molecular self-assembly takes place can be tuned, the assemblies formed under such conditions are irreversible in general . The manipulation of reversible supramolecular phase transitions requires a dynamic interface, for example, the liquid/solid interface, and at least an external stimulation is needed and applied to the system in situ .…”

Section: Resultsmentioning

confidence: 99%

Synergic Effect: Temperature-Assisted Electric-Field-Induced Supramolecular Phase Transitions at the Liquid/Solid Interface

et al. 2019

View full text Add to dashboard Cite

Using trimesic acid (TMA) as a model system by means of scanning tunneling microscope (STM) equipped with a temperature controller, here, we report a temperature-assisted method to cooperatively control electric-field-induced supramolecular phase transitions at the liquid/solid interface. Octanoic acid is used as a solvent due to its good solubility for TMA and its less complicated pattern formed under negative STM bias (e.g., only chicken-wire polymorphs existing). At positive substrate bias, STM revealed that TMA assembly based on temperature modulations underwent phase transitions from a porous (22 °C) to a flower (45 °C) and further to a zigzag (68 °C) structure. The transitions are ascribed to the partial deprotonation of the carboxyl groups of TMA. Both the temperature and electrical polarity of the substrate are crucial, i.e., the transitions only take place at positive substrate bias and elevated temperatures. Molecular mechanics simulations were carried out to calculate the temperature and electric field dependence of the adsorption enthalpy and free energy of the chicken-wire assembly of TMA on the two layers of graphene surface. The calculated decrease in adsorption enthalpy with the increase of temperature and electric field values that causes the TMA chicken-wire assembly to be less stable is proposed to promote the occurrence of the phase transition observed by STM. This study paves the way toward program-controlled supramolecular phase switching via the synergic effect of electrical and thermal stimuli.

show abstract

Section: Resultsmentioning

confidence: 99%

Synergic Effect: Temperature-Assisted Electric-Field-Induced Supramolecular Phase Transitions at the Liquid/Solid Interface

et al. 2019

View full text Add to dashboard Cite

show abstract

“…Despite its simple chemical structure, rigidity, and high symmetry, self-assembly of TMA is complex and shows rich behaviour with different surface polymorphs. [20][21][22][23][24][25][26][27][28] Yet, the so called chickenwire structure a hexagonal porous honeycomb network with a lattice parameter of ~1.7 nm and a pore diameter of ~1.0 nm is the most abundant structure (cf. inset in Fig.…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2017

View full text Add to dashboard Cite

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 such as, are moiré periodicity and orientation always the same, i.e. is exclusively only one specific moiré pattern observed? What are the geometric relationships (superstructure matrices) between moiré, TMA, and graphite lattices? What affects the moiré pattern formation? Is there any influence from solvent, concentration, or thermal treatment? These basic questions are addressed via 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 the moiré patterns is attributed to minute deviations (<2°) from this preferred orientation. Quantitative analysis of moiré periods and orientations facilitates the determination of the TMA lattice parameter with picometer precision.

show abstract

“…Directional and highly selective noncovalent interactions between functional organic molecules on solid substrates usually lead to the appearance of self-assembled molecular patterns in the adsorption overlayers (Bartels 2010;Barth 2007;Baviloliaei and Diekhöner 2014;Kühnle 2009;Marshall and Medlin 2011;Rahe et al 2012;Wang et al 2010). The formation of such ordered structures in adsorbed organic layers defines their chemical, electric, optical and biological properties.…”

Section: Introductionmentioning

confidence: 99%

Adsorption thermodynamics of cross-shaped molecules with one attractive arm on random heterogeneous square lattice

2015

View full text Add to dashboard Cite

Understanding the forces governing the arrangement of organic molecules on the solid surface is the key to control and creation of self-assembled organic nanostructures. In this paper we use the simple lattice gas model and grand canonical Monte Carlo method to demonstrate how the random surface heterogeneity affects both structural and thermodynamic properties of the adsorption overlayer of cross-shaped molecules with one attractive arm. The simulated results show that phase behavior of the adlayer on the random heterogeneous surface characterized by small energy difference between adsorption on the ''weak'' and ''strong'' sites and/or low concentration of the ''strong'' sites (0.1 and less) can be described as the hierarchical self-assembly process. On the other hand, the simulations performed for the system with large energy difference between adsorption on the ''weak'' and ''strong'' sites revealed that the stable phases appearing on the surface at coverage close to 0.5 and higher are the balance products of the ''adsorbate-adsorbate'' and ''adsorbate-substrate'' interactions.

show abstract

Molecular self-assembly at nanometer scale modulated surfaces: trimesic acid on Ag(111), Cu(111) and Ag/Cu(111)

Cited by 23 publications

References 34 publications

Synergic Effect: Temperature-Assisted Electric-Field-Induced Supramolecular Phase Transitions at the Liquid/Solid Interface

Synergic Effect: Temperature-Assisted Electric-Field-Induced Supramolecular Phase Transitions at the Liquid/Solid Interface

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

Adsorption thermodynamics of cross-shaped molecules with one attractive arm on random heterogeneous square lattice

Contact Info

Product

Resources

About