在无效的π扩展核心修饰八中进行质子合的氧转换
Tridib Sarma1,2, Gakhyun Kim3, Sajal Sen2
1Center for Supramolecular Chemistry & Catalysis , Shanghai University , Shanghai 200444 , China.
Journal of the American Chemical Society
|September 6, 2018
概括
一种新型的八氨酸经过质子合电子转移 (PCET) 进行基于氧化还原的切换. 这一发现使得新的合成系统能够通过质子化来减少两个电子.
科学领域:
- 有机化学
- 超分子化学
- 摄影化学
背景情况:
- 质子合电子转移 (PCET) 在化学和生物学中至关重要.
- 在合成氧化还原系统中,PCET具有开关的潜力.
- 在合成系统中利用PCET仍然有限.
研究的目的:
- 为基于PCET的切换开发一个核心修改的八蛋白.
- 为了研究质子合的两电子还原的机制.
- 探索质子化对氧化还原潜力的影响.
主要方法:
- 从纳夫托比皮罗尔和迪提诺提奥芬前体合成平面,弱反芳香/非芳香的八.
- 使用化物进行质子合双电子还原.
- 电化学分析以确定氧化还原潜力的转移.
- 通过X射线衍射和光谱来描述氧化和减少的形式.
主要成果:
- 在化的存在下,八氨酸经历了质子合的双电子还原.
- 在三酸中观察到一个 [4n+1] π电子中间基态.
- 质子化显著地转移了降解电位,从而促进了化离子的电子转移.
- 富含电子的分子,如TTF,PTZ和甲基醇也会诱导PCET.
结论:
- 由PCET驱动的开发的八氧作为一个可转氧系统.
- 质子化是调节八氨酸电子特性和促进电子转移的关键.
- 这项工作扩大了PCET在合成氧化还原活性材料中的应用.
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