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Self-Assembly of Decoupled Borazines on Metal Surfaces: The Role of the Peripheral Groups

机译:金属表面解耦硼嗪的自组装:外围基团的作用

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摘要

Two borazine derivatives have been synthesised to investigate their self-assembly behaviour on Au(111) and Cu(111) surfaces by scanning tunnelling microscopy (STM) and theoretical simulations. Both borazines form extended 2D networks upon adsorption on both substrates at room temperature. Whereas the more compact triphenyl borazine 1 arranges into close-packed ordered molecular islands with an extremely low density of defects on both substrates, the tris(phenyl-4-phenylethynyl) derivative 2 assembles into porous molecular networks due to its longer lateral substituents. For both species, the steric hindrance between the phenyl and mesityl substituents results in an effective decoupling of the central borazine core from the surface. For borazine 1, this is enough to weaken the molecule–substrate interaction, so that the assemblies are only driven by attractive van der Waals intermolecular forces. For the longer and more flexible borazine 2, a stronger molecule–substrate interaction becomes possible through its peripheral substituents on the more reactive copper surface.
机译:通过扫描隧道显微镜(STM)和理论模拟,合成了两种硼嗪衍生物,研究了它们在Au(111)和Cu(111)表面的自组装行为。两种硼嗪在室温下吸附在两种底物上后形成扩展的 2D 网络。更致密的三苯硼嗪 1 排列成紧密堆积的有序分子岛,在两个底物上缺陷密度极低,而三(苯基-4-苯乙炔基)衍生物 2 由于其较长的侧取代基而组装成多孔分子网络。对于这两个物种,苯基和三甲苯基取代基之间的空间位阻导致中央硼嗪核心与表面的有效解耦。对于硼嗪 1,这足以削弱分子-底物相互作用,因此组装体仅由有吸引力的范德华分子间作用力驱动。对于更长、更灵活的硼嗪 2,通过其在反应性更强的铜表面上的外围取代基,可以实现更强的分子-底物相互作用。

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