铁亚二烯的氧复合可逆异构化,通过单一的绿灯
Masato Kurihara1, Akira Hirooka, Shoko Kume
1Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Journal of the American Chemical Society
|July 26, 2002
概括
发现了一种新的绿色光驱动的meta-ferrocenylazobenzene异构化循环,利用Fe (II) 和Fe (III) 状态之间的氧化还原变化. 这个过程提供了高效的trans-to-cis和cis-to-trans光异构化,可以通过光和氧化还原状态来控制.
科学领域:
- 有机金属化学 有机金属化学
- 摄影化学的使用.
- 材料科学 材料科学 材料科学
背景情况:
- 阿佐二衍生物以其光异构化特性而闻名.
- 含铁素的分子具有独特的氧化还原和电子特性.
- 控制光异构化与外部刺激,如光和氧化还原潜力是一个关键的挑战.
研究的目的:
- 发现和描述一个新的可逆异构化循环的meta-ferrocenylazobenzene.
- 为了研究绿色光和氧化还原状态 (Fe(II) /Fe(III)) 在控制光异构化中的作用.
- 探索铁替代位置对光异构化行为的影响.
主要方法:
- 绿光 (546 nm) 辐射实验. 在绿光 (546 nm) 辐射实验.
- 电化学方法诱导Fe (II) 和Fe (III) 状态之间的氧化还原变化.
- 用光谱分析来监测异构化.
- 时间依赖密度函数理论 (TD-DFT) 的计算.
主要成果:
- 使用绿光和氧化还原切换实现了对meta-ferrocenylazobenzene的可逆异构化循环.
- 高量子产量 (Phit-->c = 0.51) 用于通过金属到联体电荷转移 (MLCT) 在Fe(II) 状态下进行跨到 cis 异体化.
- 在氧化成Fe (III) 和绿光照射时观察到的有效的cis-to-trans反反应.
- 光异构化强烈依赖于铁替代位置;MLCT激发在Para-ferrocenylazobenzene中是无效的.
- 在TD-DFT计算中,MLCT起源的meta和para-isomers之间存在差异.
结论:
- 发现的循环使得使用绿色光线对甲基-铁烯酸进行可氧化还原控制的光异构化.
- MLCT特征的"开关"对于氧化还原依赖光反应至关重要.
- 替代位置显著影响到光异构化机制和铁烯酸的效率.
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