Usingnatural photosynthesis as a model, bio-inspired constructsfor fuel generation from sunlight are being developed. Here we reportthe synthesis and time-resolved spectroscopic analysis of a moleculartriad in which a porphyrin electron donor is covalently linked toboth a cyanoporphyrin electron acceptor and a benzimidazole–phenolmodel for the TyrZ-D1His190 pair of PSII. Adual-laser setup enabled us to record the ultrafast kinetics and long-livingspecies in a single experiment. From this data, the photophysicalrelaxation pathways were elucidated for the triad and reference compounds.For the triad, quenching of the cyanoporphyrin singlet excited statelifetime was interpreted as photoinduced electron transfer from theporphyrin to the excited cyanoporphyrin. In contrast to a previousstudy of a related molecule, we were unable to observe subsequentformation of a long-lived charge separated state involving the benzimidazole–phenolmoiety. The lack of detection of a long-lived charge separated stateis attributed to a change in energetic landscape for charge separation/recombinationdue to small differences in structure and solvation of the new triad. [ABSTRACT FROM AUTHOR]