Peri-Substituted Acyl Pyrrolyl Naphthalenes: Synthesis, Reactions and Photophysical Properties

Abstract

The preparation of two 1-acyl-8-pyrrolylnaphthalenes (5 and 6) and one pyrrolone (8) are reported along with the issues complicating the preparations of other compounds. The photophysical behavior of the fused, planar derivative 6 is explored in detail. The fluorescence of 6 shows solvato-chromism due to intramolecular charge transfer in the excited state and enhanced emission in protic solvents. The emission intensity increases very linearly with the H-bond-donating strength of the solvent. Preferential solvation studies, multilinear regression analysis and computational modeling suggest that the fluorescence enhancement results from inhibition of the spin–orbit coupling-promoted intersystem crossing from the π→π* singlet state to an n→π* triplet state. Some of the inhibitions are due to the dielectric stabilization of the excited singlet state. A stronger effect is obtained from H-bonding, which not only further stabilizes the singlet state but also negatively impacts the vibronic coupling between the states.

Keywords

• solvato-chromism
• charge transfer
• peri
• pyrrole
• spin–orbit coupling