Ultrafast energy transfer and excited state coupling in an artificial photosynthetic antenna.

We have studied the energy transfer dynamics in an artificial light-harvesting dyad composed of a phthalocyanine (Pc) covalently linked to a carotenoid (Car). The combination of high temporal resolution transient absorption spectroscopy with global and target analysis allowed us to quantify the efficiency of the energy transfer from the S2 excited state of the Car to the Pc at 37%, close to values observed in some natural light-harvesting complexes. In addition, following selective excitation of the Pc, we have identified the spectral signatures of the S1 excited state of the Car which appear within the ≈30 fs time resolution of our measurement. This strongly indicates excited state coupling between the S1 state of Car and the Qx state of Pc, with important implications for the regulation of photosynthetic activity.