A Joint Theoretical and Experimental Insight into the Electronic Structure of Chromophores Derived from 6H,12H-5,11-Methanodibenzo[b,f][1,5]diazocine

We report on the synthesis and electronic spectra of the chiral, donor‐acceptor (push‐pull) chromophores (±)‐4 and (±)‐5 with a 6H,12H‐5,11‐methanodibenzo[b,f][1,5]diazocine scaffold (Scheme 1 and Fig. 2). The electronic structures of these compounds were investigated at a quantum‐chemical level (Figs. 2 and 3). The chemical reactivity of 6H,12H‐5,11‐methanodibenzo[b,f][1,5]diazocine ((±)‐11) towards aromatic electrophilic substitution (Scheme 2 and Table) provided additional information about its electronic structure and confirmed nonnegligible delocalization of the lone pair of the bridge‐head N‐atoms in this heterocyclic system.