Photochemistry of Benzophenone in Solution: A Tale of Two Different Solvent Environments,Journal of the American Chemical Society

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Photochemistry of Benzophenone in Solution: A Tale of Two Different Solvent Environments
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-09-03 , DOI: 10.1021/jacs.9b07047
Ravi Kumar Venkatraman ₁ , Andrew J Orr-Ewing ₁

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A long-standing ambition of photochemists is to excite species selectively in a complex liquid solution, and in turn instigate a controlled chemical reaction. Benzophenone (Bzp) has been studied over six decades as a model system for under-standing the photophysics and photochemistry of organic chromophores. Herein, we exploit the red-edge excitation effect to demonstrate that by sub-ensemble selective excitation of Bzp molecules, either coordinated or non-coordinated to phenol through hydrogen bonding in a dichloromethane solution, the rate of an H-atom abstraction reaction can be accelerated by a factor of ~40. To this end, we have employed femtosecond time-resolved electronic and vibrational absorption spectroscopy in conjunction with DFT/TD-DFT calculations. The outcomes have implications for deductions drawn from single-excitation-wavelength studies of the photochemistry of similar molecular systems, and especially of charge-transfer chromophores.

中文翻译：

溶液中二苯甲酮的光化学：两种不同溶剂环境的故事

光化学家的一个长期目标是在复杂的液体溶液中选择性地激发物种，进而引发受控的化学反应。二苯甲酮 (Bzp) 作为理解有机发色团光物理和光化学的模型系统已被研究了 60 多年。在此，我们利用红边激发效应证明，通过在二氯甲烷溶液中通过氢键与苯酚配位或非配位的 Bzp 分子的亚集合选择性激发，H 原子提取反应的速率可以是加速了约 40 倍。为此，我们结合 DFT/TD-DFT 计算采用了飞秒时间分辨电子和振动吸收光谱。

更新日期：2019-09-03

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