在非循环和互锁素结合受体离子识别中证明素键共价性
Sean W Robinson1, Chantal L Mustoe, Nicholas G White
1Chemistry Research Laboratory, Department of Chemistry, University of Oxford , Mansfield Road, Oxford OX1 3TA, U.K.
Journal of the American Chemical Society
|December 6, 2014
概括
新型素结合 (XB) 受体显示选择性酸盐结合和增强的离子识别. 互锁的XB [2]链因其独特的3D腔体而表现出反转化物选择性,性能优于HB类似物.
科学领域:
- 超分子化学 超分子化学
- 阳离子的识别方法
- 素结合 素结合
背景情况:
- 结合 (HB) 受体在离子识别方面受到广泛研究.
- 素结合 (XB) 为宿主-客体化学提供了一个替代的,可能更强的非共价相互作用.
- 循环和机械互锁的分子 (例如,连锁体) 存在不同的结合环境.
研究的目的:
- 为了合成和描述使用素结合的新型非循环和 [2]catenane离子宿主.
- 研究这些XB系统的离子结合特性,包括选择性和结合常量.
- 为了比较XB主机与类似的HB系统的性能,并探索机械互锁对绑定的影响.
主要方法:
- 合成含有 bis-iodotriazole-pyridinium 的新型非循环和 [2]catenane 的化合物.
- 使用UV-Vis定位和在竞争性溶剂混合物中确定关联常数的离子结合研究.
- 化物复合物的X射线晶体分析,以阐明固态相互作用.
- 射线吸收光谱 (XAS) 探测素键的电子结构和共价性.
- 密度函数理论 (DFT) 计算以支持实验发现.
主要成果:
- XB非循环受体选择性地与化物结合酸盐,与HB类似物相比,表现出增强的识别能力.
- 由于XB [2]catenane的3D腔体,而没有oxoanion结合,XB [2]catenane表现出相对于非循环XB受体的逆化物选择性.
- [2]catenane在有机水性混合物中显著增强了离子识别,与HBcatenane类似物相比.
- X射线结晶学证实了在连锁复合体中强烈的XB相互作用.
- XAS和DFT研究显示,素键具有显著的共价性,可与过渡金属坐标键相比较.
结论:
- 新的XB非循环和 [2]catenane宿主表现出可调节的离子结合选择性和增强的识别特性.
- 与非循环对应物相比,catenane中的机械互锁显著改变了化物选择性.
- 这些系统中的素键具有相当大的共价性,为离子识别设计提供了强大的工具.
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