The photophysical characterization of four supramolecular complexes based on covalent cages 2H-S-2H, 2H-L-2H, Zn-S-2H, and Zn-L-2H, consisting in either two free-base porphyrins or one Zn(II) porphyrin and one free-base porphyrin connected by four flexible linkers of different lengths incorporating triazole binding sites, and their Ag(I) complexation are reported. The complexation processes have been followed by means of absorption and emission spectroscopies, and a comprehensive computational study explains the behavior of the free-base porphyrin-containing cages. Absorption and emission features have been interpreted on the bases of conformational changes, metalation processes, and modification of energy transfer efficiencies occurring in the different cases. In all cages, except 2H-L-2H, the coordination of four Ag(I) ions to the lateral triazole groups of the linkers leads to the enlargement of their cavity. Only for 2H-L-2H is a different behavior observed, where the process of silver metalation of the porphyrins' core prevails.
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