Synthesis and properties of a triphenylene–butadiynylene macrocycle
Synthesis and properties of a triphenylene–butadiynylene macrocycle
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DOI：
10.1039/c0jm02150d
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发表时间：
2011-01
影响因子：
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通讯作者：
Henning Wettach;S. Höger;Debangshu Chaudhuri;J. Lupton;Feng Liu;Elizabeth M. Lupton;S. Tretiak;
中科院分区：
文献类型：
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作者：
Henning Wettach;S. Höger;Debangshu Chaudhuri;J. Lupton;Feng Liu;Elizabeth M. Lupton;S. Tretiak;
本文详细介绍了由两个“半环”分子间格雷偶联和适当的开环二聚体分子内偶联形成的形状恒定的三苯基-丁二炔大环的合成和表征。对光物理的研究表明，与开放二聚体相比，大环在基态的共轭程度更高，而在激发态的共轭程度更低，这是由于大环中的二乙炔由于其受限的拓扑结构而发生弯曲的结果。通过扫描隧道显微镜(STM)观察到大环上2D结构的浓度依赖性，发现大环上带有柔性侧基，支持其在高取向热解石墨(HOPG)上的吸附。灵活的侧基还保证了即使在非极性溶剂(环己烷)中也有很高的化合物溶解度。然而，动态光散射、X射线散射和原子力显微镜显示，疏溶剂相互作用导致形成管状超结构。
The synthesis and characterization of a shape-persistent triphenylene–butadiynylene macrocycle formed by intermolecular Glaser-coupling of two “half-rings” and also by intramolecular coupling of the appropriate open dimer, respectively, are described in detail. The investigation of the photophysics has revealed that—compared to its open dimer—the macrocycle is more conjugated in the ground state and less so in the excited state, a result of the diacetylene bending in the macrocycle due to its constrained topology. The macrocycle is decorated with flexible side groups that support its adsorption on highly oriented pyrolytic graphite (HOPG) where a concentration-dependence of the 2D-structure is observed by means of scanning tunnelling microscopy (STM). The flexible side groups also guarantee a high compound solubility even in nonpolar solvents (cyclohexane). However, solvophobic interactions lead to the formation of a tube-like superstructure, as revealed by dynamic light scattering, X-ray scattering and atomic force microscopy.