Blockade of persistent colored isomer formation in photochromic 3H-naphthopyrans by excited-state intramolecular proton transfer

Abstract

In photochemistry the excited-state intramolecular proton transfer process (ESIPT) is often observed as a highly efficient singlet excited state depletion pathway, which in the presence of a strong intramolecular hydrogen bond may proceed on a subpicosecond time scale. The present work describes the suppression of unwanted transoid-trans isomer formation in photochromic 3H-naphthopyran derivatives by the introduction of a 5-hydroxy substituent. According to time-resolved spectroscopy experiments and excited-state ab initio calculations, transoid-cis → transoid-trans photoisomerization is reduced by a competitive ESIPT channel in nonpolar solvent (cyclohexane). Upon specific solute–solvent interactions (methanol, acetonitrile) the intramolecular hydrogen bond in the transoid-cis form is perturbed, favoring the internal conversion S1 → S0 process as photostabilizing channel.