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

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 S-1 -> S-0 process as photostabilizing channel.

Automated summary

The introduction of a 5-hydroxy substituent can suppress the formation of unwanted transoid-trans isomers in photochromic compounds. In nonpolar solvent, competitive ESIPT pathway reduces the transoid-cis -> transoid-trans photoisomerization. Specific solute-solvent interactions favor the internal conversion as a photostabilizing channel.