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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.
Original language | English |
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Pages (from-to) | 15222-15229 |
Number of pages | 8 |
Journal | Journal of the American Chemical Society |
Volume | 141 |
Issue number | 38 |
Early online date | 3 Sep 2019 |
DOIs | |
Publication status | Published - 25 Sep 2019 |
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Benzophenone-Phenol Photochemistry
Orr-Ewing, A. J. (Creator), University of Bristol, 30 Jun 2019
DOI: 10.5523/bris.3plogqpyz66uu28y3wrzcu9p2h, http://data.bris.ac.uk/data/dataset/3plogqpyz66uu28y3wrzcu9p2h
Dataset