Modulating the electron-transfer properties of a mixed-valence system through host-guest chemistry

• Autor(a) principal: Zubi, Ahmed
• Data de Publicação: 2015
• Outros Autores: Wragg, Ashley, Turega, Simon, Adams, Harry, Costa, Paulo J., Felix, Vitor, Thomas, Jim A.
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
• Texto Completo: http://hdl.handle.net/10773/20347
• topic: INTERVALENCE CHARGE-TRANSFER; DYNAMIC COMBINATORIAL LIBRARIES; SUPRAMOLECULAR CHEMISTRY; METAL-COMPLEXES; ELECTROCHEMICAL OXIDATION; ACETONITRILE SOLUTION; TRANSFER IVCT; RECOGNITION; TRANSITION; DNA

Metal directed self-assembly has become a much-studied route towards complex molecular architectures. Although studies on mixed valence, MV, systems accessible through this approach are almost non-existent, the potential applications of such systems are very exciting as MV states provide the basis of a number of molecular-scale devices, including single electron wires and switches. Furthermore, while many novel hosts for guest ions and molecules have been developed through metal directed self-assembly, as these products tend to be kinetically labile, very few electrochemical studies have been reported. Herein, we report that the interplay between the binding properties and redox activity of a self-assembled trinuclear Ru-II macrocycle leads to an hitherto unreported phenomenon, in which access to specific MV states can be gated by host-guest chemistry. Thus, this system is the first in which MV states and the extent of electron delocalisation are switched by an ion without any change in electrochemical potential.