As the expected lifetimes of excited radical species are generally in the picosecond range, an efficient diffusion-controlled reactivity at moderate substrate concentrations cannot be achieved and a bimolecular reaction may only occur, if the two reaction partners are already pre-assembled prior to photo-excitation. Since the relaxation of the Ar 3 N •+ is facilitated mainly by rotation of the aromatic rings, we explored on the one hand if a rigid and cyclic architecture extends the excited state lifetime of the Ar 3 N •+ *, and on the other hand if this triarylamine modification will also prevent its known photo-degradation. Additionally, we examined potential pre-organisation of aryl substrates to the planar structure of Ar 3 N •+ via cation-π interaction making electron transfer more feasible.