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Issue 2, 2015
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Modulating the electron-transfer properties of a mixed-valence system through host–guest chemistry

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Abstract

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 RuII 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.

Graphical abstract: Modulating the electron-transfer properties of a mixed-valence system through host–guest chemistry

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Submitted
11 Sep 2014
Accepted
21 Nov 2014
First published
26 Nov 2014

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2015,6, 1334-1340
Article type
Edge Article
Author version available

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

A. Zubi, A. Wragg, S. Turega, H. Adams, P. J. Costa, V. Félix and J. A. Thomas, Chem. Sci., 2015, 6, 1334
DOI: 10.1039/C4SC02799J

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