超快速质子转移到溶剂:分子性和来自溶解和扩散控制模式的中间体
J L Pérez-Lustres1, F Rodriguez-Prieto, M Mosquera
1Institute for Chemistry, Humboldt University of Berlin, Brook-Taylor-Strasse 2, 12489 Berlin, Germany.
Journal of the American Chemical Society
|April 10, 2007
概括
光诱导质子转移 (PT) 是通过溶解控制的,其动态是由溶剂相互作用决定的. 一个单一的水分子.
科学领域:
- 光化学和物理化学.
背景情况:
- 光诱导的质子转移 (PT) 是化学和生物学的一个基本过程.
- 了解控制PT动态的因素对于各种应用至关重要.
研究的目的:
- 为了研究从6-基 (6HQc) 和6-基-1-基 (6MQc) 酸到水和酒精的光诱导质子转移动力学.
- 为了研究zwitterionic结合基1-methylquinolinium-6-olate (6MQz) 的溶解动力学.
主要方法:
- 静态和短暂的吸收光谱学.
- 量子化学计算 量子化学计算
- 对于溶解动态的Solvatochromic探测器和介电损耗数据.
主要成果:
- 这种6MQz的zwitterionic监测了没有分子内电子转移的溶解动态.
- 来自6HQc和6MQc离子的质子转移 (PT) 动态密切遵循溶解动态,表明了溶解控制.
- 确定了PT的2kJ/mol的低激活障碍.
- 在水中,6HQc与水分子之间的键稳定了复合体,促进了PT.
- 在乙二中,观察到一种中间的PT状态.
- 在混合溶剂中,PT之后是扩散控制反应,其中一个水分子足以进行质子分离.
结论:
- 光诱导的质子转移主要由溶解动力学控制.
- 反应机制涉及初始的键和随后的溶剂辅助质子脱离.
- 单个水分子的扩散足以驱动质子转移过程.
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