Mimicking Photosystem I with a Transmembrane Light Harvester and Energy Transfer-Induced Photoreduction in Phospholipid Bilayers.

Photosystem I (PS I) is a transmembrane protein that assembles perpendicular to the membrane, and performs light harvesting, energy transfer, and electron transfer to a final, water-soluble electron acceptor. We present here a supramolecular model of it formed by a bicationic oligofluorene 1 bound to the bisanionic photoredox catalyst eosin Y (EY ) in phospholipid bilayers. According to confocal microscopy, molecular modeling, and time dependent density functional theory calculations, 1 prefers to align perpendicularly to the lipid bilayer. In presence of EY , a strong complex is formed (K =2.1±0.1×10  m ), which upon excitation of 1 leads to efficient energy transfer to EY . Follow-up electron transfer from the excited state of EY to the water-soluble electron donor EDTA was shown via UV-Vis absorption spectroscopy. Overall, controlled self-assembly and photochemistry within the membrane provides an unprecedented yet simple synthetic functional mimic of PS I.