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Issue 39, 2014
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Transient UV pump–IR probe investigation of heterocyclic ring-opening dynamics in the solution phase: the role played by nσ* states in the photoinduced reactions of thiophenone and furanone

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Abstract

The heterocyclic ring-opening dynamics of thiophenone and furanone dissolved in CH3CN have been probed by ultrafast transient infrared spectroscopy. Following irradiation at 267 nm (thiophenone) or 225 nm (furanone), prompt (τ < 1 ps) ring-opening is confirmed by the appearance of a characteristic antisymmetric ketene stretching feature around 2150 cm−1. The ring-opened product molecules are formed highly vibrationally excited, and cool subsequently on a ∼6.7 ps timescale. By monitoring the recovery of the parent (S0) bleach, it is found that ∼60% of the initially photoexcited thiophenone molecules reform the parent molecule, in stark contrast with the case in furanone where there is less than 10% parent bleach recovery. Complementary ab initio calculations of potential energy cuts along the S–C([double bond, length as m-dash]O) and O–C([double bond, length as m-dash]O) ring-opening coordinate reveals insights into the reaction mechanism, and the important role played by dissociative (n/π)σ* states in the UV-induced photochemistry of such heterocyclic systems.

Graphical abstract: Transient UV pump–IR probe investigation of heterocyclic ring-opening dynamics in the solution phase: the role played by nσ* states in the photoinduced reactions of thiophenone and furanone

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Article information


Submitted
15 Aug 2014
Accepted
20 Aug 2014
First published
20 Aug 2014

This article is Open Access

Phys. Chem. Chem. Phys., 2014,16, 21271-21279
Article type
Paper

Transient UV pump–IR probe investigation of heterocyclic ring-opening dynamics in the solution phase: the role played by nσ* states in the photoinduced reactions of thiophenone and furanone

D. Murdock, S. J. Harris, J. Luke, M. P. Grubb, A. J. Orr-Ewing and M. N. R. Ashfold, Phys. Chem. Chem. Phys., 2014, 16, 21271
DOI: 10.1039/C4CP03653K

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