%0 Journal Article
%A Goretzki, Gudrun
%A Davies, E. Stephen
%A Argent, Stephen P.
%A Warren, John E.
%A Blake, Alexander J.
%A Champness, Neil R.
%D 2009
%T Building Multistate Redox-Active Architectures Using Metal-Complex Functionalized Perylene Bis-imides
%U https://acs.figshare.com/articles/journal_contribution/Building_Multistate_Redox_Active_Architectures_Using_Metal_Complex_Functionalized_Perylene_Bis_imides/2817043
%R 10.1021/ic901379d.s001
%2 https://ndownloader.figshare.com/files/4514629
%K perylene core
%K bisimide
%K ferrocene groups
%K acid
%K Cyclic voltammetry measurements
%K cobalt dithiolene moiety
%K communication
%K crystal
%K moietie
%K diffraction
%K disubstituted
%X 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 1−4, 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, 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.
%I ACS Publications