A Supramolecular [10]CPP Junction Enables Efficient Electron Transfer in Modular Porphyrin–[10]CPP⊃Fullerene Complexes

Efficient photoinduced electron transfer was observed across a 10]cycloparaphenylene (10]CPP) moiety that serves as a rigid non‐covalent bridge between a zinc porphyrin and a range of fullerenes. The preparation of iodo‐10]CPP is the key to the synthesis of a porphyrin–10]CPP conjugate, which binds C₆₀, C₇₀, (C₆₀)₂, and other fullerenes (K_A>10⁵ m ^?1). Fluorescence and pump–probe spectroscopy revealed intramolecular energy transfer between CPP and porphyrin and also efficient charge separation between porphyrin and fullerenes, affording up to 0.5 μs lifetime charge‐separated states. The advantage of this approach towards electron donor–acceptor dyads is evident in the case of dumbbell‐shaped (C₆₀)₂, which gave intricate charge‐transfer behavior in 1:1 and 2:1 complexes. These results suggest that 10]CPP and its cross‐coupled derivatives could act as supramolecular mediators of charge transport in organic electronic devices.