Very fast electron migrations within p-doped aromatic cofacial arrays leading to three-dimensional (toroidal) pi-delocalization.

The charge-resonance phenomenon originally identified by Badger and Brocklehurst lies at the core of the basic understanding of electron movement and delocalization that is possible within p-doped aromatic (face-to-face) arrays. To this end, we now utilize a series of different aryl-donor groups (Ar) around a central platform to precisely evaluate the intramolecular electron movement among these tethered redox centers. As such, the unique charge-resonance (intervalence) absorption bands observed upon the one-electron oxidation or p-doping of various hexaarylbenzenoid arrays (Ar6C6) provide quantitative measures of the reorganization energy (lambda) and the electronic coupling element (H(ab)) that are required for the evaluation of the activation barrier (deltaG(ET)) for electron-transfer self-exchange according to Marcus-Hush theory. The extensive search for viable redox centers is considerably aided by the application of a voltammetric criterion that has led in this study to Ar = N,N-dialkyl-p-anilinyl, in which exceptionally low barriers are shown to lie in the range deltaG(ET) = 0.3-0.7 kcal mol(-1) for very fast electron hopping or peregrination around the hexagonal circuit among six equivalent Ar sites. Therefore, at transition temperatures T(t) > 0.5/R or roughly -20 degrees C, the electron-transfer dynamics become essentially barrierless since the whizzing occurs beyond the continuum of states and effectively achieves complete pi-delocalization.