Quenching of porphyrin excited states by adjacent or distant porphyrin cation radicals in molecular arrays

The quenching of photoexcited porphyrins by porphyrin cation radicals at adjacent or distant sites in diphenylethyne-linked porphyrin dyads and triads has been studied using static and time-resolved optical spectroscopy. The excited-state quenching is highly efficient in all cases (>99%) and occurs in ⩽11 ps between adjacent sites (by through-bond energy/charge transfer) and in ⩽55 ps between distant sites (likely by superexchange-assisted energy transfer). The rates can be tuned using the porphyrin-linker connection motif. These results should prove useful in the design of arrays that use electro- or photo-chemically generated porphyrin cation radicals for molecular switching and other applications in molecular photonics.