- Self-Assembled Two-Dimensional Nanoporous Crystals as MolecularSieves: Molecular Dynamics Studies of 1,3,5-Tristyrilbenzene‑CnSuperstructures doi link

Auteur(s): St.john Alexandre, Roth M.W., Firlej L.(Corresp.), Kuchta B, Charra F., Wexler C

(Article) Publié: Journal Of Chemical Information And Modeling, vol. p.a-m (2020)

Ref HAL: hal-02512091_v1
DOI: 10.1021/acs.jcim.0c00015
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Due to their unique geometry complex, self-assembled nanoporous 2D molecular crystals offer a broad landscape ofpotential applications, ranging from adsorption and catalysis to optoelectronics, substrate processes, and future nanomachineapplications. Here we report and discuss the results of extensive all-atom Molecular Dynamics (MD) investigations of self-assembledorganic monolayers (SAOM) of interdigitated 1,3,5-tristyrilbenzene (TSB) molecules terminated by alkoxy peripheral chains Cncontaining n carbon atoms (TSB3,5-Cn) deposited onto highly ordered pyrolytic graphite (HOPG). In vacuo structural andelectronic properties of the TSB3,5-Cn molecules were initially determined using ab initio second order Møller−Plesset (MP2)calculations. The MD simulations were then used to analyze the behavior of the self-assembled superlattices, including relaxed latticegeometry (in good agreement with experimental results) and stability at ambient temperatures. We show that the intermoleculardisordering of the TSB3,5-Cn monolayers arises from competition between decreased rigidity of the alkoxy chains (loss ofintramolecular order) and increased stabilization with increasing chain length (afforded by interdigitation). We show that theinclusion of guest organic molecules (e.g., benzene, pyrene, coronene, hexabenzocoronene) into the nanopores (voids formed byinterdigitated alkoxy chains) of the TSB3,5-Cn superlattices stabilizes the superstructure, and we highlight the importance of alkoxychain mobility and available pore space in the dynamics of the systems and their potential application in selective adsorption.