Morino Kazuhide, Watase Nobuyuki, Maeda Katsuhiro, Yashima Eiji
Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan.
Chemistry. 2004 Oct 4;10(19):4703-7. doi: 10.1002/chem.200400381.
Poly[(4-carboxyphenyl)acetylene] (poly-1) exhibits an intense induced circular dichroism (ICD) in the UV-visible region upon complexation with excess (R)-1-(1-naphthyl)ethylamine ((R)-2), owing to the formation of a predominantly single-handed helical conformation of the polymer backbone. In the presence of a small amount of (R)-2, poly-1 showed a very weak ICD due to the lack of a single-handed helical conformation. However, we have found that the co-addition of the excess bulky, achiral 1-naphthylmethylamine (5) with a small amount of (R)-2 caused a dramatic increase in the ICD magnitude, comparable to the full ICD induced by excess (R)-2. This indicates that an almost single-handed helix can be induced on poly-1 upon complexation with a small amount of (R)-2 assisted by achiral 5. Furthermore, the induced single-handed helical poly-1 could be successfully memorized by the replacement of (R)-2 and 5 with achiral 2-aminoethanol or n-butylamine.
聚[(4-羧基苯基)乙炔](聚-1)在与过量的(R)-1-(1-萘基)乙胺((R)-2)络合时,由于聚合物主链形成了主要为单手螺旋构象,在紫外-可见区域表现出强烈的诱导圆二色性(ICD)。在存在少量(R)-2的情况下,由于缺乏单手螺旋构象,聚-1显示出非常弱的ICD。然而,我们发现,将过量的大体积非手性1-萘基甲胺(5)与少量(R)-2共同添加会导致ICD强度显著增加,与过量(R)-2诱导的完全ICD相当。这表明在与少量(R)-2络合时,在手性5的辅助下,聚-1上可以诱导出几乎单手的螺旋结构。此外,通过用非手性2-氨基乙醇或正丁胺取代(R)-2和5,可以成功地记忆诱导的单手螺旋聚-1。