在光色-二甲基硫氧化物复合体中的图秒异构
Aaron A Rachford1, Jeffrey J Rack
1Department of Chemistry and Biochemistry, Ohio University, Athens, Ohio 45701, USA.
Journal of the American Chemical Society
|November 2, 2006
概括
复合物与二甲基硫氧化物 (dmso) 配体经历激发状态的分子内异构. 这项研究量化了这些光活性化合物中S-to-O异构的速率和机制.
科学领域:
- 摄影化学的使用.
- 协调化学 协调化学
- 频谱学是一种光谱学.
背景情况:
- 复合物与特皮里丁 (tpy) 和双皮里丁 (bpy) 或皮里丁碳酸盐 (pic) 连接体具有光活性.
- 甲基二硫氧化物 (dmso) 配体可以经历激发状态的分子内异构.
研究的目的:
- 为了研究dmso配体在复合体中的激发状态分子内S-->O异构化.
- 为了确定这种异构化过程的动力学和机制.
主要方法:
- 皮秒瞬时吸收光谱法用于监测异构化.
- 用光谱数据的全球分析来提取时间常数.
- 收集了电化学,吸收和排放数据.
主要成果:
- 两个鲁复合体[Ru(tpy) ((bpy) ((dmso) ](2+) 和跨[Ru(tpy) ((pic) ((dmso) ](+) 呈现了比位指数的衰变动力学.
- 确定异构化时间常数为第一个复合体的1.5 ns,第二个复合体的480 ps.
- 热放松的兴奋状态被确定为特皮里丁局部 (3) MLCT状态.
结论:
- 从 (3) MLCT兴奋状态可以发生快速的断裂和结合反应.
- 这项研究提供了关于光激发的复合物的反应性的见解.
- 构建电子状态图来阐明观察到的反应性.
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