Volume increment effect on the photoisomerization of hemicyanine dyes in oligo(ethylene glycol)s.

We studied the excited-state dynamics of three hemicyanine dyes that undergo internal twisting from the localized excited state to the twisted intramolecular charge-transfer state. The dyes differ in the length of the alkyl chain in the aniline moiety and, thus, the volume of the motional moiety increases without having much of an effect on the excited-state potential surface. By employing oligo(ethylene glycol)s as a new homologous series of solvents that covers a high viscosity region, we showed that the excited-state lifetime of the hemicyanines gradually increases at any given viscosity when the size of the substituent increases. We describe our results for the solution-phase photoisomerization processes in terms of the breakdown of Stokes' law, multidimensionality, and the Hubbard relation.