Supramolecular Porphyrin Assemblies through Amidinium–Carboxylate Salt Bridges and Fast Intra‐Ensemble Excited Energy Transfer

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Abstract
Well-defined supramolecular assemblies of Zn and free-base porphyrins are constructed through the formation of amidinium–carboxylate salt bridges. A one-to-one donor–acceptor pair and a four-to-one antenna-type assembly are investigated. The steady-state and time-resolved fluorescence measurements unequivocally showed that efficient singlet–singlet excited energy transfer from the Zn–porphyrin complex to the free-base porphyrin takes place in these assemblies. Indeed, the observed energy-transfer rates in both types of assemblies are much faster than those the Förster mechanism would suggest, implying the involvement of an intermolecular through-bond mechanism.