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

Research output: Contribution to journalArticle

Original languageEnglish
Pages (from-to)15222-15229
Number of pages8
JournalJournal of the American Chemical Society
Volume141
Issue number38
Early online date3 Sep 2019
DOIs
DateAccepted/In press - 3 Jul 2019
DateE-pub ahead of print - 3 Sep 2019
DatePublished (current) - 25 Sep 2019

Abstract

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 understanding the photophysics and photochemistry of organic chromophores. Herein, we exploit the red-edge excitation effect to demonstrate that by subensemble selective excitation of Bzp molecules, either coordinated or noncoordinated 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.

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    Rights statement: This is the author accepted manuscript (AAM). The final published version (version of record) is available online via ACS Publications at 10.1021/jacs.9b07047. Please refer to any applicable terms of use of the publisher.

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