Fluorescent perylene diimide rotaxanes: spectroscopic signatures of wheel-chromophore interactions.

[2]- and [3]-rotaxanes with a tetraphenoxy perylene diimide core were synthesized. Hydrogen bonding between the wheel and the imide changes the optical properties of the perylene chromophore: the absorption and fluorescence spectra are red-shifted. The decay times of the rotaxanes are shorter in comparison with that of the axle. Single molecule fluorescence measurements reveal relatively narrow distributions of emission maxima and decay times. The averages are in agreement with ensemble measurements. The observed red shifts make the perylene diimide a suitable chromophore for sensing the position of the wheel on the axle.