The Substituent-Induced Symmetry-Forbidden Electronic Transition Allows Significant Optical Limiting under Weak Sky-Blue Irradiance.

We report a novel material containing a rare metal-free dopant chromophore with controlled electronic symmetry, which exhibits strong optical limiting (OL) capabilities under weak, continuous, sky-blue irradiance. Electron-donating substituents at positions C2 and C7 of pyrene allow significant triplet generation because of the symmetrically forbidden transition between the ground state and the lowest singlet excited state, which leads to accumulation of triplet excitons in the dopant chromophore. This also leads to a small ground state absorption coefficient and induces greater absorption of sky-blue wavelengths when triplet excitons of the chromophore accumulate. Consequently, molecular glass doped with the designed chromophore displays stronger OL characteristics compared with those of the rare element-containing glass that previously demonstrated the greatest OL performance under continuous sky-blue irradiance at sunlight power levels. The described approach to developing cost-effective, state-of-the-art OL materials is crucial for nonlinear optical applications working at a large scale under sunlight or room lights.