| Abstrakt: |
Due to their unique geometry complex, self-assembled nanoporous 2D molecular crystals offer a broad landscape of potential applications, ranging from adsorption and catalysis to optoelectronics, substrate processes, and future nanomachine applications. Here we report and discuss the results of extensive all-atom Molecular Dynamics (MD) investigations of self-assembled organic monolayers (SAOM) of interdigitated 1,3,5-tristyrilbenzene (TSB) molecules terminated by alkoxy peripheral chains Cncontaining ncarbon atoms (TSB3,5-Cn) deposited onto highly ordered pyrolytic graphite (HOPG). In vacuostructural and electronic properties of the TSB3,5-Cnmolecules were initially determined using ab initiosecond order Møller–Plesset (MP2) calculations. The MD simulations were then used to analyze the behavior of the self-assembled superlattices, including relaxed lattice geometry (in good agreement with experimental results) and stability at ambient temperatures. We show that the intermolecular disordering of the TSB3,5-Cnmonolayers arises from competition between decreased rigidity of the alkoxy chains (loss of intramolecular order) and increased stabilization with increasing chain length (afforded by interdigitation). We show that the inclusion of guest organic molecules (e.g., benzene, pyrene, coronene, hexabenzocoronene) into the nanopores (voids formed by interdigitated alkoxy chains) of the TSB3,5-Cnsuperlattices stabilizes the superstructure, and we highlight the importance of alkoxy chain mobility and available pore space in the dynamics of the systems and their potential application in selective adsorption. |
