RESUMO
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.
Assuntos
Ciclodextrinas/química , Compostos Organometálicos/química , Eletrodos Seletivos de Íons , Luz , Substâncias Macromoleculares , Modelos Químicos , Técnicas de Sonda Molecular , Estrutura Molecular , FotoquímicaRESUMO
Layer-by-layer deposition of π-assembled arrays of discrete metallo units with aryl tails and polystyrenesulfonate gives structurally well-defined thin films. The formation of these films, which is controlled by π-π interactions, metal-ion coordination, and electrostatic interactions, bridges the gap between supramolecular crystal engineering and design of layered materials.
