Unusual Photophysical Properties of Porphyrin-Based Supramolecular Polymers Unveiled: The Role of Metal Ligands and...

Supramolecular polymers based on porphyrins are an interesting model system, since the self-assembly and thus the photophysics can be modified by the chemical structure of the porphyrins, e.g., by a metal inserted in the ligand or by different (solubilizing) side groups. Here, we investigate the photophysical properties of supramolecular polymers based on free-base and Zn-centered porphyrins, each with different amide connectivity in the side chains, by absorption and (time-resolved) photoluminescence spectroscopy on solutions. We find that for all porphyrin derivatives the B-band absorption of supramolecular polymers is a superposition of H- and J-type aggregate spectra, while the Q-band absorption indicates only J-type aggregation. The emission of supramolecular polymers stems exclusively from the Q-band and shows only J-type behavior. For supramolecular polymers based on the free-base porphyrins, we identify only a single aggregate species, whereas for Zn-centered porphyrins, two distinct species coexist in solution, each with a (slightly) different arrangement of monomers. We rationalize this complex behavior by a slip-stacking of porphyrins along the direction of one of the two B-band transition dipole moments, resulting in simultaneous H- and J-type intermolecular coupling in the B-band. In the Q-band, with its transition dipole moments oriented 45° relative to the corresponding B-band moments, only J-type coupling is thus present. Our results demonstrate that the self-assembly and the photophysics of supramolecular polymers based on porphyrins can only be fully understood if spectral information from all bands is considered.