以预先设计的双宏循环受体和离子为导向的自组
De-Hui Tuo1,2, Wei Liu1, Xue-Yuan Wang1,2
1Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry , Chinese Academy of Sciences , Beijing 100190 , China.
Journal of the American Chemical Society
|December 19, 2018
概括
研究人员创建了能够产生离子-π 相互作用的新型双环分子. 这些分子自我组装成有序的结构,通过腔的方向来控制粒子的形成和形态.
科学领域:
- 超分子化学
- 材料科学
- 有机化学
背景情况:
- 阴离子-π 相互作用对于自我组装至关重要,但对于中性受体来说很难实现.
- 控制超分子结构的组合和形态是材料科学的关键目标.
研究的目的:
- 为离子驱动的自组装设计和合成新型比索卡利克[2]二烯[2]三基.
- 研究连接器刚性和分支角度对分子识别和自我组装行为的影响.
- 通过这些双宏环成分来探索有序聚合物的形成和控制它们的形态.
主要方法:
- 合成具有不同链接体几何形状的比索卡利克斯[2][2].
- 用X射线结晶学来确定分子结构和腔的方向.
- 溶液相结合研究 (例如1H NMR定位) 以评估宿主-客体相互作用.
- 在溶液中研究聚合的光谱技术 (DOSY,ESI-MS) 和散射方法 (DLS).
- 显微镜技术 (SEM,TEM,冷TEM,AFM) 用于可视化自组装结构.
主要成果:
- 刚性链接器成功控制了bisoxacalix[2]arene[2]triazines中的宏环腔的方向.
- 主体分子表现出选择性结,对180°和120°分支异构体进行双复合.
- 与甲-1,5-二硫酸盐的阳离子相互作用诱导了远程自组合和连贯颗粒的形成.
- 宏观循环腔的方向显著影响了所产生的粒子的形态.
结论:
- 比索卡利克斯[2][2]是离子诱导自组合的有效基石.
- 分子设计,特别是连接器刚性和分支,决定了结合特性和自我组装结果.
- 阴离子-π 相互作用在桥接宿主聚合物和指导有序超分子结构的形成中至关重要.
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