Self-assembly of decoupled borazines on metal surfaces: the role of the peripheral groups.
Self-assembly of decoupled borazines on metal surfaces: the role of the peripheral groups.
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DOI：
10.1002/chem.201402839
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发表时间：
2014-09-08
期刊：
影响因子：
--
通讯作者：
Costantini G
中科院分区：
文献类型：
--
作者：
Kalashnyk N;Ganesh Nagaswaran P;Kervyn S;Riello M;Moreton B;Jones TS;De Vita A;Bonifazi D;Costantini G
合成了两种环硼氮烷衍生物，利用扫描隧道显微镜（STM）和理论模拟研究了它们在Au（111）和Cu（111）表面的自组装行为。两种环硼氮烷在室温下吸附在两种基底上时形成扩展的2D网络。而更紧凑的三苯基环硼氮烷1安排成紧密堆积有序的分子岛上的两个基板上的缺陷密度极低，三（苯基-4-苯乙炔基）衍生物2组装成多孔分子网络，由于其较长的横向取代基。对于这两个物种，苯基和mesityl取代基之间的空间位阻的结果在一个有效的解耦中心环硼氮烷核心从表面。对于环硼氮烷1来说，这足以削弱分子与基底的相互作用，使得组装体仅由吸引的范德华货车分子间力驱动。对于更长和更灵活的环硼氮烷2，更强的分子-基底相互作用成为可能，通过其周边的取代基上的更具反应性的铜表面。
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.
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