Guest-Mediated Modulation of Photophysical Pathways in a Coronene Bisimide Cyclophane

The properties and functions of chromophores utilized by nature are strongly affected by the environment formed by the protein structure in the cells surrounding them. This concept is transferred here to host-guest complexes with the encapsulated guests acting as an environmental stimulus. A new cyclophane host based on coronene bisimide is presented that can encapsulate a wide variety of planar guest molecules with binding constants up to (4.29 ± 0.32) × 10¹⁰ M^-1 in chloroform. Depending on the properties of the chosen guest, the excited state deactivation of the coronene bisimide chromophore can be tuned by the formation of host-guest complexes toward fluorescence, exciplex formation, charge separation, room-temperature phosphorescence (RTP), or thermally activated delayed fluorescence (TADF). The photophysical processes were investigated by UV/vis absorption, emission, and femto- and nanosecond transient absorption spectroscopy. To enhance the TADF, two different strategies were used by employing suitable guests: the reduction of the singlet-triplet gap by exciplex formation and the external heavy atom effect. Altogether, by using supramolecular host-guest complexation, a versatile multimodal chromophore system is achieved with the coronene bisimide cyclophane.