Covalently linked cyclic porphyrin arrays have been synthesized to mimic natural light-harvesting apparatuses and to investigate the highly efficient energy migration processes occurring in these systems for future applications in molecular photonics. To avoid an ensemble-averaged picture, we performed a single-molecule spectroscopic study on the energy migration processes of cyclic porphyrin arrays and a linear model compound embedded in a rigid polymer matrix by recording fluorescence intensity trajectories, by performing coincidence measurements, and by doing wide-field defocused imaging. Our study demonstrates efficient energy migration within the cyclic porphyrin arrays at the single-molecule level. By comparison with the data of the linear model compound, we could pinpoint the role of the dipole-dipole coupling between diporphyrin subunits and the rigidity of the cyclic structures on the energy transfer processes.
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