title: Perchlorination of Coronene Enhances its Propensity for Self-Assembly on Graphene.
abstract: Providing a quantitative understanding of the thermodynamics involved in molecular adsorption and self-assembly at a nanostructured carbon material is of fundamental importance and finds outstanding applications in the graphene era. Here, we study the effect of edge perchlorination of coronene, which is a prototypical polyaromatic hydrocarbon, on the binding affinity for the basal planes of graphite. First, by comparing the desorption barrier of hydrogenated versus perchlorinated coronene measured by temperature-programmed desorption, we quantify the enhancement of the strength of physisorption at the single-molecule level though chlorine substitution. Then, by a thermodynamic analysis of the corresponding monolayers based on force-field calculations and statistical mechanics, we show that perchlorination decreases the free energy of self-assembly, not only enthalpically (by enhancing the strength of surface binding), but also entropically (by decreasing the surface concentration). The functional advantage of a chemically modulated 2D self-assembly is demonstrated in the context of the molecule-assisted liquid-phase exfoliation of graphite into graphene.
authors.affiliation: Laboratoire d'Ingénierie des Fonctions Moléculaires, ISIS & icFRC, Université de Strasbourg & CNRS, 8 allée Gaspard Monge, 67000, Strasbourg (France.
authors.forename: Simone
authors.identifier: http://orcid.org/0000-0001-7986-567X
authors.initials: S
authors.lastname: Conti
authors.affiliation: Nanochemistry Laboratory, ISIS & icFRC, Université de Strasbourg & CNRS, 8 allée Gaspard Monge, 67000, Strasbourg (France.
authors.forename: Maria G
authors.identifier: http://orcid.org/0000-0002-0704-7747
authors.initials: MG
authors.lastname: del Rosso
authors.affiliation: Nanochemistry Laboratory, ISIS & icFRC, Université de Strasbourg & CNRS, 8 allée Gaspard Monge, 67000, Strasbourg (France.
authors.forename: Artur
authors.identifier: http://orcid.org/0000-0003-3542-4092
authors.initials: A
authors.lastname: Ciesielski
authors.affiliation: Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 2, 76131, Karlsruhe (Germany.
authors.forename: Jürgen
authors.identifier: http://orcid.org/0000-0002-5597-5767
authors.initials: J
authors.lastname: Weippert
authors.affiliation: Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 2, 76131, Karlsruhe (Germany.
authors.forename: Artur
authors.identifier: http://orcid.org/0000-0001-8477-1336
authors.initials: A
authors.lastname: Böttcher
authors.affiliation: School of Chemistry, University of Manchester, Oxford road, Manchester, M13 9PL (UK.
authors.forename: Yuyoung
authors.identifier: http://orcid.org/0000-0003-4359-5406
authors.initials: Y
authors.lastname: Shin
authors.affiliation: Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), UMR 7504, 23, rue du Loess, 67037 Cedex 08, Strasbourg (France.
authors.forename: Georgian
authors.initials: G
authors.lastname: Melinte
authors.affiliation: Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), UMR 7504, 23, rue du Loess, 67037 Cedex 08, Strasbourg (France.
authors.forename: Ovidiu
authors.initials: O
authors.lastname: Ersen
authors.affiliation: School of Chemistry, University of Manchester, Oxford road, Manchester, M13 9PL (UK.
authors.forename: Cinzia
authors.identifier: http://orcid.org/0000-0001-7185-0377
authors.initials: C
authors.lastname: Casiraghi
authors.affiliation: Max Plank Institute for Polymer Research, Ackermannweg 10, 55128, Mainz (Germany.|Center for Advancing Electronics Dresden (CFAED) & Department of Chemistry and Food Chemistry, Technische Universitaet Dresden, 01062, Dresden (Germany.
authors.forename: Xinliang
authors.initials: X
authors.lastname: Feng
authors.affiliation: Max Plank Institute for Polymer Research, Ackermannweg 10, 55128, Mainz (Germany.
authors.forename: Klaus
authors.initials: K
authors.lastname: Müllen
authors.affiliation: Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 2, 76131, Karlsruhe (Germany. manfred.kappes@kit.edu.
authors.forename: Manfred M
authors.initials: MM
authors.lastname: Kappes
authors.affiliation: Nanochemistry Laboratory, ISIS & icFRC, Université de Strasbourg & CNRS, 8 allée Gaspard Monge, 67000, Strasbourg (France. samori@unistra.fr.
authors.forename: Paolo
authors.identifier: http://orcid.org/0000-0001-6256-8281
authors.initials: P
authors.lastname: Samorì
authors.affiliation: Laboratoire d'Ingénierie des Fonctions Moléculaires, ISIS & icFRC, Université de Strasbourg & CNRS, 8 allée Gaspard Monge, 67000, Strasbourg (France. mcecchini@unistra.fr.
authors.forename: Marco
authors.identifier: http://orcid.org/0000-0003-2671-1583
authors.initials: M
authors.lastname: Cecchini
keywords: graphene; interfaces; polycyclic aromatic hydrocarbons; self-assembly; statistical thermodynamics