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Photochemistry of Benzophenone in Solution: A Tale of Two Different Solvent Environments

Research output: Contribution to journalArticle

Original languageEnglish
JournalJournal of the American Chemical Society
DateAccepted/In press - 3 Sep 2019

Abstract

A long-standing ambition of photochemists is to excite species selectively in a complex liquid solution, and in turn insti-gate 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 absorp-tion 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.

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