Transforming Dyes into Fluorophores: Exciton‐Induced Emission with Chain‐like Oligo‐BODIPY Superstructures

Herein we present a systematic study demonstrating to which extent exciton formation can amplify fluorescence based on a series of ethylene‐bridged oligo‐BODIPYs. A set of non‐ and weakly fluorescent BODIPY motifs was selected and transformed into discrete, chain‐like oligomers by linkage via a flexible ethylene tether. The prepared superstructures constitute excitonically active entities with non‐conjugated, Coulomb‐coupled oscillators. The non‐radiative deactivation channels of Internal Conversion (IC), also combined with an upstream reductive Photoelectron Transfer (rPET) and Intersystem Crossing (ISC) were addressed at the monomeric state and the evolution of fluorescence and (non‐)radiative decay rates studied along the oligomeric series. We demonstrate that a “masked” fluorescence can be fully reactivated irrespective of the imposed conformational rigidity. This work challenges the paradigm that a collective fluorescence enhancement is limited to sterically induced motional restrictions.