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

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Reversible Anion-Driven Switching of an Organic 2D Crystal at a Solid–Liquid Interface. / Cui, K.; Mali, K.S.; Wu, D. et al.

In: Small, Vol. 13, No. 46, 1702379, 13.12.2017.

Research output: Contribution to Journal/MagazineJournal articlepeer-review

Harvard

Cui, K, Mali, KS, Wu, D, Feng, X, Müllen, K, Walter, M, De Feyter, S & Mertens, SFL 2017, 'Reversible Anion-Driven Switching of an Organic 2D Crystal at a Solid–Liquid Interface', Small, vol. 13, no. 46, 1702379. https://doi.org/10.1002/smll.201702379

APA

Cui, K., Mali, K. S., Wu, D., Feng, X., Müllen, K., Walter, M., De Feyter, S., & Mertens, S. F. L. (2017). Reversible Anion-Driven Switching of an Organic 2D Crystal at a Solid–Liquid Interface. Small, 13(46), [1702379]. https://doi.org/10.1002/smll.201702379

Vancouver

Cui K, Mali KS, Wu D, Feng X, Müllen K, Walter M et al. Reversible Anion-Driven Switching of an Organic 2D Crystal at a Solid–Liquid Interface. Small. 2017 Dec 13;13(46):1702379. Epub 2017 Sep 27. doi: 10.1002/smll.201702379

Author

Cui, K. ; Mali, K.S. ; Wu, D. et al. / Reversible Anion-Driven Switching of an Organic 2D Crystal at a Solid–Liquid Interface. In: Small. 2017 ; Vol. 13, No. 46.

Bibtex

@article{2d280f0100a94a08b867ad369440f7a6,
title = "Reversible Anion-Driven Switching of an Organic 2D Crystal at a Solid–Liquid Interface",
abstract = "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 6 + ) 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. {\textcopyright} 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",
keywords = "adlayer, adsorption, anion, ionic self-assembly, switching, Adsorbates, Adsorption, Biomimetic materials, Biomimetics, Catalysis, Crystal structure, Density functional theory, Design for testability, Electrostatic force, Inorganic compounds, Negative ions, Phase interfaces, Positive ions, Scanning tunneling microscopy, Self assembly, Supramolecular chemistry, Switching, Vapor deposition, Adlayers, Adsorbate interactions, Ionic self- assembly, Molecular building blocks, Self assembled structures, Supramolecular arrangement, Supramolecular interactions, Two-dimensional (2D) crystals, Ions",
author = "K. Cui and K.S. Mali and D. Wu and X. Feng and K. M{\"u}llen and M. Walter and {De Feyter}, S. and S.F.L. Mertens",
year = "2017",
month = dec,
day = "13",
doi = "10.1002/smll.201702379",
language = "English",
volume = "13",
journal = "Small",
issn = "1613-6810",
publisher = "Wiley-VCH Verlag",
number = "46",

}

RIS

TY - JOUR

T1 - Reversible Anion-Driven Switching of an Organic 2D Crystal at a Solid–Liquid Interface

AU - Cui, K.

AU - Mali, K.S.

AU - Wu, D.

AU - Feng, X.

AU - Müllen, K.

AU - Walter, M.

AU - De Feyter, S.

AU - Mertens, S.F.L.

PY - 2017/12/13

Y1 - 2017/12/13

N2 - 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 6 + ) 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. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

AB - 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 6 + ) 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. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

KW - adlayer

KW - adsorption

KW - anion

KW - ionic self-assembly

KW - switching

KW - Adsorbates

KW - Adsorption

KW - Biomimetic materials

KW - Biomimetics

KW - Catalysis

KW - Crystal structure

KW - Density functional theory

KW - Design for testability

KW - Electrostatic force

KW - Inorganic compounds

KW - Negative ions

KW - Phase interfaces

KW - Positive ions

KW - Scanning tunneling microscopy

KW - Self assembly

KW - Supramolecular chemistry

KW - Switching

KW - Vapor deposition

KW - Adlayers

KW - Adsorbate interactions

KW - Ionic self- assembly

KW - Molecular building blocks

KW - Self assembled structures

KW - Supramolecular arrangement

KW - Supramolecular interactions

KW - Two-dimensional (2D) crystals

KW - Ions

U2 - 10.1002/smll.201702379

DO - 10.1002/smll.201702379

M3 - Journal article

VL - 13

JO - Small

JF - Small

SN - 1613-6810

IS - 46

M1 - 1702379

ER -