Dianion and Dication of Tetracyclopentatetraphenylene as Decoupled Annulene-within-an-Annulene Models

The dianion and dication of tetramesityl-substituted tetracyclopentatetraphenylene, a circulene consisting of alternating five- and six-membered rings, have been generated by reduction with alkali metals and oxidation with antimony(V) halides, respectively. They are theoretically predicted to adopt double annulenoid structures called annulene-within-an-annulene models in which the outer and inner conjugation circuits are significantly decoupled. The theoretical structures were experimentally proven by X-ray crystallographic analyses and the electronic configurations were supported by MCD spectra. Based on the C-13 NMR chemical shifts, negative and positive charges are shown to be located mainly at the outer periphery, indicating that the dianion and dication have delocalized 22-pi and 18-pi electron outer perimeters, respectively, and 8-pi electron structure at the inner ring. Notably, the dianion has an open-shell character, whereas the dication has a closed-shell ground state.