Solvent induced conformer specific photochemistry of guaiacol

Literature Information

Publication Date 2014-06-18
DOI 10.1039/C4CP02424A
Impact Factor 3.676
Authors

Simon E. Greenough, Michael D. Horbury, James O. F. Thompson, Gareth M. Roberts, Tolga N. V. Karsili, Barbara Marchetti, Dave Townsend, Vasilios G. Stavros


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Abstract

Using a combination of ultrafast solution- and gas-phase spectroscopies, together with high-level theory calculations, we demonstrate that we are able to track conformer-specific photodissociation dynamics in solution through solvent choice. We reveal this phenomenon in guaiacol (2-methoxyphenol), a key subunit of the natural biopolymer lignin. In cyclohexane, the first electronically excited 1ππ* (S1) state in guaiacol relaxes with a time-constant of τ = 4.5 ± 0.2 ns, mediated through intersystem crossing to lower lying triplet (Tn) states and internal conversion and fluorescence back to the ground state (S0). In contrast, in methanol, a further relaxation channel is also present; the S1 state relaxes with a time-constant of τ = 2.9 ± 0.1 ns, which is now additionally mediated through coupling onto a dissociative 1πσ* (S2) state and subsequent O–H bond fission, evidenced through the appearance of a spectral signature for the guaiacoxyl radical after ∼250 ps. With the aid of complementary calculations, we attribute this to the now absent intramolecular H-bond between OH and OMe moieties, which now favours intermolecular H-bonding to methanol, lowering the barrier to O–H dissociation and facilitating H-atom loss via tunnelling.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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