Institute of Organic Chemistry III/Macromolecular Chemistry.
Beilstein J Nanotechnol. 2011;2:405-15. doi: 10.3762/bjnano.2.46. Epub 2011 Jul 26.
The position of the peripheral nitrogen atoms in bis(terpyridine)-derived oligopyridines (BTPs) has a strong impact on their self-assembly behavior at the liquid/HOPG (highly oriented pyrolytic graphite) interface. The intermolecular hydrogen bonding interactions in these peripheral pyridine units show specific 2D structures for each BTP isomer. From nine possible constitutional isomers only four have been described in the literature. The synthesis and self-assembling behavior of an additional isomer is presented here, but the remaining four members of the series are synthetically inaccessible. The self-assembling properties of three of the missing four BTP isomers can be mimicked by making use of the energetically preferred N-C-C-N transoid conformation between 2,2'-bipyridine subunits in a new class of so-called septipyridines. The structures are investigated by scanning tunneling microscopy (STM) and a combination of force-field and first-principles electronic structure calculations.
在双（三联吡啶）衍生的寡聚吡啶（BTP）中，外围氮原子的位置对它们在液体/ HOPG（高取向热解石墨）界面处的自组装行为有很强的影响。这些外围吡啶单元中的分子间氢键相互作用为每个 BTP 异构体呈现出特定的 2D 结构。在这 9 种可能的结构异构体中，只有 4 种在文献中有描述。本文介绍了一种额外异构体的合成和自组装行为，但该系列的其余 4 种成员在合成上无法获得。通过利用新一类所谓的 septipyridines 中 2,2'-联吡啶单元之间的能量上优先的 N-C-C-N 反式构象，可以模拟出这四个缺失的 BTP 异构体中的三个的自组装特性。通过扫描隧道显微镜（STM）和力场与第一性原理电子结构计算的组合对结构进行了研究。
