Electronic Communication through π-Conjugated Wires in Covalently Linked Porphyrin/C60 Ensembles

Novel photo‐ and electroactive triads, in which π‐conjugated p‐phenylenevinylene oligomers (oPPVs) of different length are connected to a photoexcited‐state electron donor (i.e., zinc tetraphenylporphyrin) and an electron acceptor (i.e., C60), were designed, synthesized, and tested as electron‐transfer model systems. A detailed physicochemical investigation, concentrating mainly on long‐range charge separation and charge recombination and kinetics, revealed small attenuation factors βof 0.03±0.005 Å−1. Energy matching between the HOMO levels of C60and oPPVs emerged as a key parameter for supporting molecular‐wire‐like behavior: It favors rapid and efficient electron or hole injection into the oPPV wires. Large electronic coupling values were determined as a result of paraconjugation in the oPPV moieties.