Aggregation of an n-pi* Molecule Induces Fluorescence Turn-on

Abstract

Although n-π∗ molecules can serve as electroluminescent materials because of the harvesting of singlet and triplet excitons through El-Sayed-rule-allowed reverse intersystem crossing, the weak fluorescence emissions of such molecules have prevented applications into devices. We have discovered a 1 order of magnitude enhancement of the fluorescence of a prototypical n-π∗ fluorophore, 7-phenylcoumarin (PC), upon aggregation. We performed a mechanistic study consisting of structural, photophysical, and quantum chemical investigations, and found that the aggregation positioned the fluorescent electronic state below the nonemissive triplet n-π∗ transition state. Our studies, for the first time, demonstrate intramolecular geometry and intermolecular arrangements in the solid state to be significant factors in the photoluminescence quantum yields of n-π∗ fluorophores. © 2017 American Chemical Society.