Experimental Evidence for a Highly Reversible Excited State Equilibrium between s-Cis and s-Trans Rotational Isomers of 2-Methoxynaphthalene in Solution

摘要

Detailed studies on the kinetics and the thermodynamics of the excited-state torsional isomerization of the title molecule (1) relative to exocyclic C2-O bond, when dissolved in 3-methylpentane, are reported by means of nontime- and time-resolved fluorescence spectroscopy. Over the broad temperature range studied, 1 exists in spectrally distinct, thermally equilibrated s-cis and s-trans conformations in the ground state (S_0). In the lowest excited singlet state (S_1) and above 260 K a pure adiabatic interconversion channel is activated that interconverts s-cis~* and s-trans~* conformers through a nearly fully reversible isomerization pathway with an activation energy of about 29 kJ/mol. The excited-state equilibrium constant is found to be remarkably temperature-independent just barely exceeding 1 above 260 K. Contrary to the predominantly irreversible photoisomerization mechanism generally observed in related compounds, this work provides insights into the high reversibility of an excited-state rotameric equilibration in solution.