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一个封闭的分子篮子的设计,合成和结构动力学
Veselin Maslak1, Zhiqing Yan, Shijing Xia
1Department of Chemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, USA.
Journal of the American Chemical Society
|April 28, 2006
概括
合成和研究了动态分子容器1-3. 化合物1主要以单体的形式存在,在平衡状态下有多个与结合的合体,其中占主导地位的是合体1a. 容器1选择性地结合了.
科学领域:
- 超分子化学 超分子化学
- 有机合成 有机合成
- 物理化学 物理化学
背景情况:
- 动态分子容器对于分子识别和封装至关重要.
- 了解它们的结构动态和结合性质是设计新功能系统的关键.
- 之前的研究已经探讨了各种宿主-客化学物质,但动态容器的详细构造分析仍然是一个活跃的领域.
研究的目的:
- 合成和描述新的动态分子容器 (1-3).
- 研究这些容器在溶液中的构造性行为和聚合性质.
- 阐明宿主-客人识别特性,特别是的结合.
主要方法:
- 分子容器的合成 1-3.
- 使用1HNMR稀释,扩散NMR和蒸气压度法进行溶液状态表征.
- 可变温度1HNMR和IR光谱学用于研究键和形态平衡.
- 计算方法包括分子力学和初始计算 (PM3,HF/6-31G) 进行结构分析.
- 单晶X射线衍射以确定固态结构.
主要成果:
- 化合物1具有较低的分子间聚合,主要存在于稀释的甲溶液中的单体.
- 可变温度的NMR和IR研究证实了在平衡状态下1和3的多个对应物的存在,它们在结合上有所不同.
- 计算研究确定了1的四个符合者,其中1a是最稳定和最占优势的.
- 合规体混合物的计算IR频谱与实验频谱相匹配,支持1a的主导地位.
- 容器1的腔体与相补充,而2的X射线结晶学显示了结合的分子.
结论:
- 合成的动态分子容器 (1-3) 具有不同的形状偏好.
- 符合1a是容器1的溶液中占主导地位的物种,由特定的结合模式驱动.
- 容器1显示了的选择性识别和结合,由腔腔互补性和实验证据表明.
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