Mimicking the Energy Funnel of the Photosynthetic Unit Using a Dendrimer-Dye Supramolecular Assembly.

Abstract

Photosynthesis involves light-harvesting complexes where an array of antenna pigment channels the absorbed solar energy to the reaction centre of a photosystem. This work reports a supramolecular dendrimer-dye assembly that mimics the natural light-harvesting mechanism. A dendrimeric molecule based on two-fluorophores has been constructed with three coumarin units at the end of three long arms and a 7-diethylaminocoumarin unit at the interior. The molecule self-aggregates in water into spherical micelles, which can encapsulate a rose-bengal dye (RB). On excitation, peripheral coumarin units shuttled the energy to the loaded RB dye reaction center via a two-step cascade resonance energy transfer (RET). The energy absorbed in the periphery is funnelled efficiently, resulting in a strong emission from the dye that resembles an energy funnel. The energy transfer cascade has been studied with both steady-state and time-resolved fluorescence spectroscopy. Molecular dynamics simulations of the self-assembled aggregates in water were also in agreement with the experimental observations.