Rerouting Electron Transfer in Molecular Assemblies by Redox-Pair Matching

We demonstrate how the distance over which electron transfer occurs through organic materials can be controlled and extended. Coating of conductive surfaces with nanoscale layers of redox‐active metal complexes allows the electrochemical addressing of distant layers that are otherwise electrochemica...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2015-10, Vol.54 (42), p.12457-12462
Main Authors: Balgley, Renata, Shankar, Sreejith, Lahav, Michal, van der Boom, Milko E.
Format: Article
Language:English
Subjects:
Assemblies
Bidirectional
Charge transfer
Coordination compounds
electrochemistry
Electron affinity
Electron transfer
metal complexes
Metals
Molecular structure
Nanostructure
redox mediators
Spacers
thin films
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Summary:We demonstrate how the distance over which electron transfer occurs through organic materials can be controlled and extended. Coating of conductive surfaces with nanoscale layers of redox‐active metal complexes allows the electrochemical addressing of distant layers that are otherwise electrochemically silent. Our materials can pass electrons selectively in directions that are determined by positioning of layers of metal complexes and the distances between them. These electron‐transfer processes can be made dominantly uni‐ or bidirectional. The design involves 1) a set of isostructural metal complexes with different electron affinities, 2) a scalable metal–organic spacer, and 3) a versatile assembly approach that allows systematic variation of composition, structure, and electron‐transfer properties. We control the electrochemical communication between interfaces by the deposition sequence and the spacer length, therefore we are able to program the bulk properties of the assemblies. Alternative routes: Variation of the positioning of redox‐active metal complexes with respect to a conductive surface leads to molecular materials with unique electron‐transfer properties. Restricted, unidirectional, and bidirectional charge transfer is obtained with the correct combination of metal complexes in well‐defined orientations (see picture).
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201505290