Photofunctional cyclophane host–guest systems

Modulation of optical properties through smart protein matrices is exemplified by a few examples in nature such as rhodopsin (absorption wavelength tuning) and the green fluorescence protein (emission), but in general, the scope found in nature for the matrix-controlled photofunctions remains rather limited. In this review, we present cyclophane-based supramolecular host-guest complexes for which electronic interactions between the cyclophane host and mostly planar aromatic guest molecules can actively modulate excited-state properties in a more advanced way involving both singlet and triplet excited states. We begin by highlighting photofunctional host-guest systems for on-off fluorescence switching and chiroptical functions using bay-functionalized perylene bisimide cyclophanes. Next, we examine the impact of π-extension in perylene bisimide cyclophanes for multiple guest binding, showcasing photofunctional properties including circularly polarized luminescence (CPL). We then focus on triplet-generating cyclophanes, i.e. coronene bisimide cyclophane, with high intersystem crossing (ISC) rates, where we demonstrate modulation of excited state pathways upon guest encapsulation and triplet sensitization through phosphorescence and thermally activated delayed fluorescence (TADF). Furthermore, using supramolecular strategies, we advance non-covalent designs, involving either heavy-atom-based Pt(acac)₂ guests or heavy-atom free charge transfer complexes, for triplet harvesting under ambient conditions and demonstrate the role of supramolecular nanoenvironments in stabilizing triplet excitons in aerated solutions. Additionally, we showcase examples for triplet-triplet annihilation (TTA) upconversion in defined cyclophane complexes in aqueous solutions and the application of host-guest chemistry in organic light-emitting diodes (OLEDs).