Photoactive metallocyclodextrins: sophisticated supramolecular arrays for the construction of light activated...

The introduction of photoactive metal centres onto cyclodextrin receptors opens up new possibilities for the design of sensors, wires and energy conversion systems. This tutorial review focuses on strategies involving such metallocyclodextrins for the construction of supramolecular arrays with light-activated functions. The assembly procedures for building such arrays are presented, together with the features required for their functions both as sensors for ion or small molecule detection and as wires for photoinduced long-range energy or electron transport. Systems for metal ion sensing are described where the cyclodextrin plays a mediating role in influencing the luminescence properties of an organic probe, responsive to metal binding. Small molecule sensing by the cyclodextrin cavity is realised using luminescent lanthanide or transition metal functionalised cyclodextrins. The light signal of the photoactive metal is switched on or off upon binding an analyte in the cyclodextrin cavity. The metallocyclodextrin systems that function as wires are distinguished by the controlled assembly of transition metal polypyridine and metalloporphyrin units. These units have inherent photoactivity that defines the vectorial direction of energy or electron transfer processes through the wire.