离子对结合中的静电和合作性:用--乙烯宏循环进行定量和合实验理论研究
Bo Qiao1, Arkajyoti Sengupta1, Yun Liu1
1Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States.
Journal of the American Chemical Society
|July 25, 2015
概括
研究人员使用--乙醇宏循环 (MC) 量化了离子对结合的合作性. 艾洛斯特里对合作性做出了重大贡献,指导了盐处理的选择性离子对受体的设计.
科学领域:
- 超分子化学
- 物理化学
- 计算化学
背景情况:
- 离子对与受体的合作结合对于盐的操纵至关重要,但人们对其了解甚少.
- 现有的模型缺乏对和静电学对合作性的全面理解.
- 设计有效的离子对受体需要详细了解结合机制.
研究的目的:
- 用实验和理论来量化离子对结合的合作性.
- 区分和理解和静电学对合作性的相对贡献.
- 建立用于增强离子对受体功能的设计原则.
主要方法:
- 半灵活的单环亚利乙醇宏循环 (MC) 的设计和合成.
- 使用NaX结合的多平衡模型对合作性 (α) 的实验量化.
- 密度函数理论 (DFT) 计算和连续性溶解模型来分析静电和度贡献.
主要成果:
- 对与MC结合的NaI (α = 1300) 和NaClO4 (α = 400) 的合作性的实验量化.
- 计算分析显示,对整体积极合作性的贡献大约为30%.
- 内在的离子大小决定了静电合作性,较小的离子表现出不同于简单的库伦定律所预测的趋势.
结论:
- 半灵活的宏循环可以促进离子对结合的最佳静电合作性.
- 离子的有效电荷在结合时被稀释,这解释了库伦定律的偏差.
- 这项工作为选择性离子对受体的合理设计提供了关键的见解.
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