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.