反氧反应性H键:使用质子合电子转移放大电子转移的效果
Hyejeong Choi1, Kiyeol Baek1, Sean T Toenjes1
1Department of Chemistry and Biochemistry, San Diego State University, San Diego, California 92182-1030, United States.
Journal of the American Chemical Society
|September 28, 2020
概括
一种新的策略利用质子合电子转移来创建氧化还原反应的键二极体. 这种方法通过电子诱导的质子转移显著增强结合强度,从而产生更强的离子键.
科学领域:
- 超分子化学
- 电化学
- 有机化学
背景情况:
- 键 (H键) 二极体在分子识别中至关重要.
- 二次 H 键对 H 键二极体的总结强度有显著的影响.
- 通过外部刺激控制H键二元稳定性是一个关键的挑战.
研究的目的:
- 提出并演示一种新策略,用于创建高氧化反应的H-键二极体.
- 为了利用质子合电子转移 (PCET) 来调节H键二极体的稳定性.
- 研究二次H键在PCET驱动的结合增强中的作用.
主要方法:
- 电活性供体-接受体-供体 (DAD) 阵列 (H(MQ+) 和电无活性接受体-供体-接受体 (ADA) 阵列 (O(NH) 的设计和合成.
- 核磁共振 (NMR) 定位以确定初始结合常数 (Kassoc).
- 循环电压测量 (CV) 来研究氧化还原行为和减少时的结合变化.
主要成果:
- 在氧化状态下,H:O:NH:O二元体呈现出典型的500M−1的卡索克.
- 两个电子的减少导致结合强度增加了1.8×105倍.
- 减少状态显示卡索克为9 × 107 M-1,这是强大的DDD-AAA H键二极体的特征,表明质子转移.
结论:
- 拟议的PCET策略有效地产生高氧化反应的H键二极体.
- 电子转移触发了质子转移,显著加强了H键相互作用.
- 这种方法为设计可切换的分子识别系统提供了强大的方法.
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