复合物:相互作用的分子识别,Möbius芳香性和性
Hervé Ruffin1, Gildas Nyame Mendendy Boussambe1, Thierry Roisnel1
1Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, Université de Rennes 1 , 263 avenue du Général Leclerc, 35042 Rennes cedex, France.
Journal of the American Chemical Society
|September 14, 2017
概括
研究人员开发了用于高级分子识别的新型顶六. 这些莫比乌斯芳香化合物具有选择性金属结合和性诱导,使其在传感和催化中具有新的应用.
科学领域:
- 超分子化学
- 有机化学
- 材料科学
背景情况:
- 六氨酸支架具有超出氨酸的独特拓,芳香性和金属协调性.
- 由于缺乏创建复杂宿主的多功能合成策略,使用六氨酸的分子识别研究是有限的.
研究的目的:
- 开发一种通用的合成策略来制造复杂的六氨基基基分子宿主.
- 研究新型六氨酸衍生物的分子识别能力.
主要方法:
- 合成后修改一个中2-氨基) 三替代平台以三脚单位封顶六甲,如三2-氨基乙 (tren).
- 由此产生的顶六氨酸的特征,包括它们在化和连接物结合时的形状变化.
- 使用奇拉氨基配体对奇拉诱导和奇拉光学特性进行评估.
主要成果:
- 在三个步骤中合成了Tren-capped hexaphyrins,表现为28π结合系统.
- Zn(II) 金属化诱导了平面到扭曲的形状变化,将系统从Hückel反芳香转变为Möbius芳香,同时保持π重叠.
- 观察到乙和氨基联体与的选择性和合作性结合,通过单元质子调节进行全调.
- 使用奇拉氨基配体实现了高奇拉诱导 (高达77%的二聚体过量),从而产生强大的圆形二元化信号.
结论:
- 开发的合成方法提供了对复杂的六氨酸宿主进行分子识别的机会.
- 铁素覆盖的六氨酸表现出可调节的电子特性和选择性客体结合,模仿金属酶活性位点.
- 这些Möbius芳香化合物显示出在奇拉感应和催化中的应用潜力.
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