The essential features of the experimental Soret bands of two covalent cages, consisting of two zincporphyrins connected by four flexible spacers, are for the first time interpreted and characterized at a molecular level by means of a mixed quantum/classical procedure based on molecular dynamics (MD) simulation and the perturbed matrix method (PMM). The same method allows also for a comprehensive interpretation of the changes in the UV− visible absorbance of the cages upon silver(I) complexation to the peripheral binding sites. Although the zinc-to-zincdistance is found to be similar in both cages, the MD-PMM calculations show that the conformation adopted by the cage with longer linkers corresponds to more slipped porphyrins, giving rise to a red-shifted (7−8 nm), broader, and slightly split Soret peak with respect to the cage with shorter linkers. The process of silver(I) complexation separates the two porphyrins in a face-to-face conformation in both cages, resulting in narrower (and more similar) Soret bands due to a reduced excitonic coupling. Despite the similar features of the spectra of the two silver(I)complexed cages, a slight difference in the peak maxima of about 2 nm is observed, arising from a slightly shorter zinc-to-zinc distance in the cage with longer linkers. These results show that the MD-PMM methodology is a reliable method to obtain information on the relative disposition and exciton coupling interaction of porphyrins in flexible systems in solution, from the analysis of their absorption spectra.

The allosteric control of the receptor properties of two flexible covalent cages is reported. These receptors consist of two zinc(II) porphyrins connected by four linkers of two different sizes, each incorporating two 1,2,3‐triazolyl ligands. Silver(I) ions act as effectors, responsible for an on/off encapsulation mechanism of neutral guest molecules. Binding silver(I) ions to the triazoles opens the cages and triggers the coordination of pyrazine or the encapsulation of N,N′‐dibutyl‐1,4,5,8‐naphthalene diimide. The X‐ray structure of the silver(I)‐complexed receptor with short connectors is reported, revealing the hollow structure with a cavity well‐defined by two eclipsed porphyrins. Rather unexpectedly, the crystallographic structure of this receptor with pyrazine as a guest molecule showed that the cavity is occupied by two pyrazines, each binding to the zinc(II) porphyrin in a monotopic fashion.

In-depth photophysical studies of four flexible covalent cages bearing either two free-base porphyrins or one free-base porphyrin and one Zn(II) porphyrin, connected by linkers of different lengths, are reported. In the case of the cages with two free-base porphyrins, exciton coupling between the porphyrins is evidenced by large and split Soret bands in the absorption spectra, but the different length of the linkers has only a slight effect on their emission properties. Strong electronic interactions between the porphyrins are also evidenced for the cages that incorporate a free-base porphyrin and a Zn(II) porphyrin, with a more pronounced splitting of the Soret band for the system with longer linkers. In these cages, following excitation of the Zn-porphyrin component, an almost quantitative energy transfer to the free-base unit occurs, with a rate 1.4 times faster in the cage with longer linkers (1.4 × 10[Formula: see text] s[Formula: see text] vs. 1.0 × 10[Formula: see text] s[Formula: see text]. This difference might reflect the more flattened conformation adopted by the cage equipped with longer and more flexible linkers, the latter allowing for a shorter interplanar distance between the porphyrins. The results are discussed in terms of classical and short-range energy transfer mechanisms.