Ultrafast Resonance Energy Transfer in Ethylene-Bridged BODIPY Heterooligomers: From Frenkel to Forster Coupling Limit

A series of distinct BODIPY heterooligomers (dyads, triads, and tetrads) comprising a variable number of typical green BODIPY monomers and a terminal red-emitting styryl-equipped species acting as an energy sink was prepared and subjected to computational and photophysical investigations in solvent media. An ethylene tether between the single monomeric units provides a unique foldameric system, setting the stage for a systematic study of excitation energy transfer processes (EET) on the basis of nonconjugated oscillators. The influence of stabilizing beta-ethyl substituents on conformational space and the disorder of site energies and electronic couplings was addressed. In this way both the strong (Frenkel) and the weak (Forster) coupling limit could be accessed within a single system: the Frenkel limit within the strongly coupled homooligomeric green donor subunit and the Forster limit at the terminal heterosubstituted ethylene bridge. Femtosecond transient-absorption spectroscopy combined with mixed quantum-classical dynamic simulations demonstrate the limitations of the Forster resonance energy transfer (FRET) theory and provide a consistent framework to elucidate the trend of increasing relaxation lifetimes at higher homologues, revealing one of the fastest excitation energy transfer processes detected to date with a corresponding lifetime of 39 fs.

Automated summary

A series of BODIPY heterooligomers were prepared and investigated for their excitation energy transfer processes, demonstrating both strong and weak coupling limits. The impact of stabilizing beta-ethyl substituents on conformational space and electronic couplings was addressed, revealing one of the fastest excitation energy transfer processes detected to date. Transient-absorption spectroscopy combined with dynamic simulations provided a consistent framework to elucidate the limitations of Förster resonance energy transfer theory.