Building multistate redox-active architectures using metal-complex functionalized perylene bis-imides

A serles 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-bisimldes. 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-1,7-diferrocenul-perylene3,4:9,10- 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-dl-(n-butyl)-1,7-dicyclopentadienylcobalt(II)-dithiolenyl-perylene-3,4:9, 10-tetracarboxylic acid bisimide (4), reveals the expected twisting of the perylene core and confirms the ene-dithlolate geometry of the cobalt dithlolene moiety. Cyclic voltammetry measurements, coupled with spectroelectrochemcial and electron paramagnetic resonance studies, of 1-4, where 1 is N,N-di(n-butyl)-l ,7-diethynylferrocenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide, reveal the two anticipated perylenebisimide based reductions. In addition, for the ferrocene substituted compounds, 1-3, 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. © 2009 American Chemical Society.