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Building Multistate Redox-Active Architectures Using Metal-Complex Functionalized Perylene Bis-imides

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journal contribution
posted on 02.11.2009 by Gudrun Goretzki, E. Stephen Davies, Stephen P. Argent, John E. Warren, Alexander J. Blake, Neil R. Champness
A series of multistate redox-active architectures has been synthesized, structurally characterized, and their optical and redox properties investigated. Specifically, two redox-active ferrocene or cobalt-dithiolene moieties have been introduced to the “bay” region of perylene-bisimides. Three of these disubstituted perylene-bisimide species have been structurally characterized by single crystal X-ray diffraction, confirming the twisted nature of the central perylene core. The first isomeric pair of disubstituted perylene-bisimide isomers, N,N′-di-(n-butyl)-1,7-diferrocenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide (2) and N,N′-di-(n-butyl)-1,6-diferrocenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide (3), structurally characterized by single crystal X-ray diffraction are reported and compared. Structural characterization of the cobalt-dithiolene substituted perylene-bisimide, N,N′-di-(n-butyl)-1,7-dicyclopentadienyl-cobalt(II)-dithiolenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide (4), reveals the expected twisting of the perylene core and confirms the ene-dithiolate geometry of the cobalt dithiolene moiety. Cyclic voltammetry measurements, coupled with spectroelectrochemcial and electron paramagnetic resonance studies, of 14, where 1 is N,N′-di-(n-butyl)-1,7-diethynylferrocenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide, reveal the two anticipated perylene-bisimide based reductions. In addition, for the ferrocene substituted compounds, 13, a single reversible two-electron oxidation is seen with only a small degree of communication between the ferrocene groups observed in the 1,6-isomer where the two ferrocene groups are attached to the same naphthyl moiety. In the case of 4, two reversible reductions associated with the cobalt-dithiolene moieties are observed, confirming communication across the reduced perylene core.