Intramolecular Charge Transfer in Antiaromatic Donor/Acceptor‐Fused <i>s</i>‐Indacenes
Isabella S. Demachkie, Michael P. Miller, Gabrielle I. Warren, Joshua E. Barker, Eric T. Strand, Lev N. Zakharov, Michael M. Haley
Abstract
Herein we report the synthesis and characterization of four donor/acceptor-fused s-indacenes via the late-stage oxidation of a family of unsymmetrical benzofuran/benzothiophene-s-indacene regioisomers. A thorough study of their properties through experimental and computational analysis has revealed the effect of asymmetry on the molecular properties associated with antiaromaticity, as well as a strong correlation between antiaromaticity and intramolecular charge transfer (ICT). The strength of the charge transfer depends on the fusion orientation of the donor and acceptor motifs relative to the s-indacene core. The two most antiaromatic oxidized isomers exhibit strong evidence of ICT with 30 and 40 nm solvatochromic shifts.