Potential-driven molecular tiling of a charged polycyclic aromatic compound

Cui, Kang; Ivasenko, Oleksandr; Mali, Kunal S.; Wu, Dongqing; Feng, Xinliang; Müllen, Kläus; Feyter, Steven De; Mertens, Stijn F. L.

doi:10.1039/c4cc04189e

Cited by 20 publications

(17 citation statements)

References 23 publications

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“…68,70 Thus bulk graphene or GRO sheets spontaneously agglomerate and even restack to form graphite or GO when left unprotected. 108 Several protocols have been reported regarding the homogeneous dispersion, chemical functionalization, and applications of modified graphite oxides (GO) or graphene oxides, such as synthesis of graphene oxide paper like materials 114 and thin films, 115 the ability of modified GO to recognize aromatic molecules 116 for controlling the aggregation state and orientation of organic dyes as well as their application as anode materials for lithium batteries. 117 Other than this, modified GO was also used for water purification in a recent example.…”

Section: Modified Graphite Oxide (Go)mentioning

confidence: 99%

Graphene based metal and metal oxide nanocomposites: synthesis, properties and their applications

et al. 2015

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Section: Modified Graphite Oxide (Go)mentioning

confidence: 99%

Graphene based metal and metal oxide nanocomposites: synthesis, properties and their applications

et al. 2015

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“…They have been triggered by pH, 38,39 light, 40 or electrochemical potential. 41,42 In our system, 43 switching was stimulated by the addition of anions and found to switch by the use of electric fields from the proximal STM tip. The cores of the molecular monomers were designed to have a single rigid conformation so that the bi-phasic behavior can be derived from changes in the supramolecular interactions, both electrostatic and vdW.…”

Section: Introductionmentioning

confidence: 80%

Living on the edge: Tuning supramolecular interactions to design two-dimensional organic crystals near the boundary of two stable structural phases

Hirsch

McDonald

Flood

et al. 2015

The Journal of Chemical Physics

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One of the benefits of supramolecular assemblies that form at dynamic interfaces is the opportunity to develop condensed phase systems that respond to environmental stimuli. A prerequisite of this responsive behavior is that the supramolecular system be designed to sit very near the stability of two or more crystal structures. We have created such a bi-phasic system with aryl-triazole oligomers by investigating how phase morphology is controlled by the interplay between interactions that involve the oligomer's dipolar cores (Δμ = 3.5 debye), van der Waals contacts of their pendant alkyl chains (C4-C18), and close-contact hydrogen bonding. Scanning tunneling microscopy experiments conducted at the solution-graphite interface allow sub-molecular resolution of the ordered monolayers to unambiguously determine the packing and structure of two principle phases, α and β. The system is balanced very near the edge of phase stability, evidenced by co-existent phases present over short time frames and by the changes in preference between the two 2D supramolecular assemblies that occur with small modifications to the molecular structure. We demonstrate that the bi-phasic behavior can be understood as a balance between electrostatic interactions and van der Waals contacts, two variables within a larger parameter space, allowing synthetic design to move this solution-surface system across the stability boundary of different condensed-phase structures. These findings are a foundation for the development of environmentally responsive 2D supramolecular arrays.

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“…In a previous report on PQPs, bias‐dependent structural transformations of the adlayer were demonstrated. In two further reports, both under electrochemical conditions, the observed self‐assembled structures were dominated by the cation and the externally applied interfacial potential. The lesser role of the anions under electrochemical conditions can be understood as in aqueous environment, both ions are strongly solvated by a solvent with high permittivity and therefore relatively independent.…”

Section: Introductionmentioning

confidence: 85%

“…Here, we report STM results of PQPs at the Au(111)/octanoic acid interface. Compared to the previously discussed electrochemical experiments, this choice of solvent imposes three important constraints on the system: first, the target molecules are soluble in octanoic acid, providing a more straightforward deposition than through dropcasting. Secondly, the static dielectric constant of octanoic acid is lower by a factor 30 than that of water (2.5 versus 80.3 at 20 °C) .…”

Section: Introductionmentioning

confidence: 99%

Reversible Anion‐Driven Switching of an Organic 2D Crystal at a Solid–Liquid Interface

Cui

Mali

et al. 2017

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Ionic self-assembly of charged molecular building blocks relies on the interplay between long-range electrostatic forces and short-range, often cooperative, supramolecular interactions, yet has been seldom studied in two dimensions at the solid-liquid interface. Here, we demonstrate anion-driven switching of two-dimensional (2D) crystal structure at the Au(111)/octanoic acid interface. Using scanning tunneling microscopy (STM), three organic salts with identical polyaromatic cation (PQPC ) but different anions (perchlorate, anthraquinonedisulfonate, benzenesulfonate) are shown to form distinct, highly ordered self-assembled structures. Reversible switching of the supramolecular arrangement is demonstrated by in situ exchange of the anion on the pre-formed adlayer, by changing the concentration ratio between the incoming and outgoing anion. Density functional theory (DFT) calculations reveal that perchlorate is highly mobile in the adlayer, and corroborate why this anion is only resolved transiently in STM. Surprisingly, the templating effect of the anion persists even where it does not become part of the adlayer 2D fabric, which we ascribe to differences in stabilization of cation conformations by the anion. Our results provide important insight into the structuring of mixed anion-cation adlayers. This is essential in the design of tectons for ionic self-assembled superstructures and biomimetic adaptive materials and valuable also to understand adsorbate-adsorbate interactions in heterogeneous catalysis.

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Potential-driven molecular tiling of a charged polycyclic aromatic compound

Abstract: Electrochemical potential causes molecular tiling of organic ions at the solid–liquid interface with supramolecular motifs that contain between 2 and 7 tectons.

Cited by 20 publications

References 23 publications

Graphene based metal and metal oxide nanocomposites: synthesis, properties and their applications

Graphene based metal and metal oxide nanocomposites: synthesis, properties and their applications

Living on the edge: Tuning supramolecular interactions to design two-dimensional organic crystals near the boundary of two stable structural phases

Reversible Anion‐Driven Switching of an Organic 2D Crystal at a Solid–Liquid Interface

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