Perchlorination of Coronene Enhances its Propensity for Self-Assembly on Graphene

Simone Conti, Maria G. Del Rosso, Artur Ciesielski, Jürgen Weippert, Artur Böttcher, Yuyoung Shin, Georgian Melinte, Ovidiu Ersen, Cinzia Casiraghi, Xinliang Feng, Klaus Müllen, Manfred M. Kappes, Paolo Samorì, Marco Cecchini

    Research output: Contribution to journalArticlepeer-review


    © 2016 Wiley-VCH Verlag GmbH & Co. KGaA.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.
    Original languageEnglish
    Pages (from-to)352-357
    Number of pages6
    Issue number3
    Publication statusPublished - 3 Feb 2016


    • graphene
    • interfaces
    • polycyclic aromatic hydrocarbons
    • self-assembly
    • statistical thermodynamics


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