Solvent induced conformer specific photochemistry of guaiacol

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 (T_n) states and internal conversion and fluorescence back to the ground state (S₀). In contrast, in methanol, a further relaxation channel is also present; the S ₁ 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. This journal is