皇冠以太复合体中的宿主内部π-π相互作用通过冷离子运动质谱学揭示
Ryosuke Ito1, Keijiro Ohshimo1, Fuminori Misaizu1
1Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan. ohshimo@tohoku.ac.jp.
Physical chemistry chemical physics : PCCP
|April 15, 2024
概括
低温离子流动性质谱学显示,宿主内部的π-π相互作用稳定了与金属离子的dinaphtho-24-crown-8 (DN24C8) 复合体. 这些相互作用对于封闭式适配器稳定性来说比主机-客力更为关键.
科学领域:
- 超分子化学 超分子化学
- 物理化学 物理化学
- 计算化学计算化学
背景情况:
- 迪纳弗托-24-皇冠-8 (DN24C8) 是一种宏环宿主分子,在分子识别中具有潜在的应用.
- 了解DN24C8复合物与金属离子的结构偏好对于设计选择性结合剂至关重要.
- 之前的研究已经探索了金属离子与皇冠结合,但在DN24C8中宿主内部相互作用的具体作用仍然不太清楚.
研究的目的:
- 调查与金属酸 (Li+,Na+,K+,Rb+,Cs+) 复合的迪纳夫托-24-皇冠-8 (DN24C8) 复合物的相对丰度.
- 通过分析宿主-客人和宿主内部相互作用,阐明观察到的"封闭"符合者的稳定性的起源.
- 为了比较DN24C8复合体的结构稳定性和相互作用区域与二-24-皇冠-8复合体的结构稳定性.
主要方法:
- 低温离子移动性质谱法 (KIMS) 用于分析金属酸-DN24C8复合体在86K的对应体.
- 密度函数理论 (DFT) 的计算被用来单独分析宿主-客和宿主内部的非共价相互作用.
- 符合性体内的π-π相互作用区域被量化并与不同的复合体进行比较.
主要成果:
- 对于所有金属阴阳复合体在86K时,主要观察到"封闭"的适配体,其特点是烯环之间的距离很短.
- 密度函数理论计算显示,宿主内部的π-π相互作用在稳定封闭的适合体中起到的作用比宿主与客之间的相互作用更为关键.
- 与dbenzo-24-crown-8类似的复合物相比,金属阴离子-DN24C8复合物的闭合合体表现出更广泛的π-π相互作用区域.
结论:
- 主体内部的π-π相互作用是金属-DN24C8复合体中闭合体稳定的主要驱动力.
- 由于DN24C8的独特结构及其扩展的甲系统,增强了π-π相互作用,从而导致更大的形状稳定性.
- 这些发现为宏循环宿主分子识别机制提供了宝贵的见解,并可以指导设计具有定制性质的新宿主分子.
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