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

被引:38
作者
Goretzki, Gudrun [1 ]
Davies, E. Stephen [1 ]
Argent, Stephen P. [1 ]
Warren, John E. [2 ]
Blake, Alexander J. [1 ]
Champness, Neil R. [1 ]
机构
[1] Univ Nottingham, Sch Chem, Nottingham NG7 2RD, England
[2] Synchrotron Radiat Source, Daresbury Lab, Warrington WA4 4AD, Cheshire, England
基金
英国工程与自然科学研究理事会;
关键词
HALF-WAVE POTENTIALS; BISIMIDE DYES; ELECTRON-TRANSFER; ENDOR SPECTROSCOPY; FLUORESCENT DYES; REDUCTION; FERROCENE; DIIMIDES; ELECTROCHEMISTRY; ACETONITRILE;
D O I
10.1021/ic901379d
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
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-dicyclopentadienylcobalt(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 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.
引用
收藏
页码:10264 / 10274
页数:11
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