Photophysics of Calix[4]biscrown-Based Ditopic Receptors of Caesium Containing One or Two Dioxocoumarin Fluorophores

The ditopic receptors Calix-COU1 and Calix-COU2 consist of a calix[4]biscrown containing one or two dioxycoumarin fluorophores, respectively, inserted into the crown. They can form 1:1 and 2:1 (metal:ligand) complexes with caesium ions. The photophysical properties of the 1:1 complexes can be explained by (i) cation tunneling through the tube-shaped cavity (composed of the four phenyl rings) of the calix[4]biscrown, (ii) photodisruption of the interaction between the bound cation and the oxygen atoms belonging to both the coumarin moiety and the crown, (iii) photoinduced motions of the cation.