Antiaromatic Spacer-Bridged Bisfluorenyl Dications Generated by Superacid Induced Ionization

Abstract

Derivatives of the dication of tetrabenzo[5.5]fulvalene were prepared with phenyl and ethynyl spacers through ionization of the appropriate bis-methylethers. The antiaromaticity shown by the parent dication was demonstrated for these dications with spacers, although it was attenuated by the presence of the spacer. It was substantially greater than that of fluorenyl monocations with similar substituents. Antiaromaticity was evaluated through comparison of (1)H NMR shifts with those of acyclic analogues, through nucleus independent chemical shifts, and through magnetic susceptibility exaltation. Although the fluorenyl systems are separated by spacers, the antiaromaticity of one system is affected by the other remote fluorenyl system. An explanation for this interaction may lie in the ability of a remote cationic substituent to attenuate delocalization in the spacer. The use of spacers is designed to prevent side reactions in less stable antiaromatic dications, allowing exploration of a number of species that have previously been inaccessible.