Electron-transfer reactions of hexaamino benzene derivatives

Hexaamino benzenes were discussed as precursors for organic ferromagnetic and non-linear optical materials. An important aspect is the redox activity of such molecules. We have studied the interaction of electron transfer and structure, as well as the influence of the substituents on the stability and reactivity of oxidized intermediates (radical cations, aminyl radicals, intrenium ions, dications).
Starting from single units, we also characterized "dimeric" molecules with two hexaamino benzene moieties. In most cases, inverted two-electron-transfers comprise the first oxidation step, which is followed by additional oxidations (up to hexacations).
In the case of the sandwich molecule, a splitting of the two-electron wave is observed, indicating increased electronic interaction between the two hexaamino benzene rings.

This project is based on an earlier cooperation with J.J. Wolff, Heidelberg (deceaded) and Gloria M. Quintanilla, Madrid, Spain.

Coworkers in this project:

Reinhard Mayer and Marc Würde

We acknowledge funding of various aspects of this project by the Deutsche Forschungsgemeinschaft, Bonn - Bad Godesberg, and the land Baden-Württemberg within a Landesforschungsschwerpunkt.

Oral presentations:

Bernd Speiser at the

59th ISE Annual Meeting, Sevilla/Spain, Sept. 7-12, 2008, keynote lecture

Publications from this project:

J.J. Wolff, A. Zietsch, B. Nuber, F. Gredel, B. Speiser und M. Würde, J. Org. Chem., 66, 2769 - 2777 (2001); Electrochemistry of Polyaminobenzenes. Part 3. Hexaaminobenzene Derivatives: Synthesis and Unusual Oxidation Behavior.

B. Speiser, M. Würde und M.G. Quintanilla, Electrochem. Commun., 2, 65 - 68 (2000); Electrochemistry of Polyaminobenzenes. Part 2. Oxidation of Hexakis(dimethylamino)benzene at High Potentials.

B. Speiser, M. Würde und C. Maichle-Mössmer, Chem. Eur. J., 4, 222 - 233 (1998); Electrochemistry of Polyaminobenzenes, Part 1. Electrochemical Oxidation of Hexakis(dimethylamino)benzene.