Abstract: | [18]‐ and [24]Annulenes condensed with three pyrene or phenanthrene ring systems show, in solution, especially in apolar solvents, a strong aggregation evidenced, for example, by concentration‐dependent 1H‐NMR spectra. However, the fluorescence bands and the fluorescence lifetimes of these compounds depend only to a minor extent on the concentration and correspond essentially to the measurements obtained for the monomer. Among several models discussed, one is favored in which aggregates can be excited, but the emission is due to an almost undisturbed monomer. Even for the pyrene system, an excimer fluorescence cannot be detected. Nevertheless, short‐lived excimers are responsible for the regio‐ and stereoselective photodimerization to belt cyclophanes. |