Surface-controlled reversal of the selectivity of halogen bonds

Jalmar Tschakert, Qigang Zhong, Daniel Martin-Jimenez, Jaime Carracedo-Cosme, Carlos Romero-Muñiz, Pascal Henkel, Tobias Schlöder, Sebastian Ahles, Doreen Mollenhauer, Hermann A. Wegner, Pablo Pou, Rubén Pérez, André Schirmeisen and Daniel Ebeling ()
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Jalmar Tschakert: Institute of Applied Physics (IAP), Justus Liebig University Giessen
Qigang Zhong: Institute of Applied Physics (IAP), Justus Liebig University Giessen
Daniel Martin-Jimenez: Institute of Applied Physics (IAP), Justus Liebig University Giessen
Jaime Carracedo-Cosme: Quasar Science Resources S.L.
Carlos Romero-Muñiz: Departamento de Física Teórica de la Materia Condensada, Universidad Autónoma de Madrid
Pascal Henkel: Center for Materials Research (LaMa), Justus Liebig University Giessen
Tobias Schlöder: Center for Materials Research (LaMa), Justus Liebig University Giessen
Sebastian Ahles: Center for Materials Research (LaMa), Justus Liebig University Giessen
Doreen Mollenhauer: Center for Materials Research (LaMa), Justus Liebig University Giessen
Hermann A. Wegner: Center for Materials Research (LaMa), Justus Liebig University Giessen
Pablo Pou: Departamento de Física Teórica de la Materia Condensada, Universidad Autónoma de Madrid
Rubén Pérez: Departamento de Física Teórica de la Materia Condensada, Universidad Autónoma de Madrid
André Schirmeisen: Institute of Applied Physics (IAP), Justus Liebig University Giessen
Daniel Ebeling: Institute of Applied Physics (IAP), Justus Liebig University Giessen

Nature Communications, 2020, vol. 11, issue 1, 1-8

Abstract: Abstract Intermolecular halogen bonds are ideally suited for designing new molecular assemblies because of their strong directionality and the possibility of tuning the interactions by using different types of halogens or molecular moieties. Due to these unique properties of the halogen bonds, numerous areas of application have recently been identified and are still emerging. Here, we present an approach for controlling the 2D self-assembly process of organic molecules by adsorption to reactive vs. inert metal surfaces. Therewith, the order of halogen bond strengths that is known from gas phase or liquids can be reversed. Our approach relies on adjusting the molecular charge distribution, i.e., the σ-hole, by molecule-substrate interactions. The polarizability of the halogen and the reactiveness of the metal substrate are serving as control parameters. Our results establish the surface as a control knob for tuning molecular assemblies by reversing the selectivity of bonding sites, which is interesting for future applications.

Date: 2020
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DOI: 10.1038/s41467-020-19379-4

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