在一个M4L6四面体宿主中,客人交换动态
Anna V Davis1, Dorothea Fiedler, Georg Seeber
1Department of Chemistry, University of California, Berkeley, 94720-1460, USA.
Journal of the American Chemical Society
|January 26, 2006
概括
这项研究定义了[Ga(4) L(6) ](12-) 超分子囊的宿主-客人动态行为. 客人交换通过一个不间断的机制发生,费率受到客人集中度和主机灵活性的影响.
科学领域:
- 超分子化学 超分子化学
- 协调化学 协调化学
- 材料科学 材料科学 材料科学
背景情况:
- M(4) L(6) 超分子组件通过不断机制促进客户交换.
- [Ga(4) L(6) ](12-) 组件,其中L = 1,5-bis(2',3'-dihydroxybenzamido) naphthalene,可以作为研究宿主-客人动态的模型系统.
研究的目的:
- 为了定义[Ga(4) L(6) ](12-) 超分子囊的宿主-客人动态行为.
- 阐明客人交换的机制,包括激活参数和客人集中度和主机灵活性的影响.
主要方法:
- 在不同的温度和压力下测量了客人自我交换率.
- 对不同的四基客体确定了激活参数 (DeltaH,DeltaS,DeltaV).
- 分析了客人移位反应,以评估客人结合亲缘关系和度的影响.
主要成果:
- 观察到阴性DeltaS和阳性DeltaV值,表明受约束的过渡状态和客人交换期间的体积增加.
- 最初的客人的出行是以PEt的价格决定的 (((4) ((+)) 换取NET (((4) ((+)).
- 由于外体相互作用的宿主灵活性下降,客人度的增加抑制了交换,这可以通过阻断外体站点来克服.
结论:
- 在[Ga(4)L(6)](12-) 组合中,客人交换对客人集中度,宿主灵活性和热力学结合亲和关系敏感.
- 外向客人的互动显著影响主机动态和客人的汇率.
- 了解这些动力学对于设计功能超分子材料至关重要.
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