Résumé : 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 derealization of the lone pair of the bridge-head N-atoms in this heterocyclic system. © 2007 Verlag Helvetica Chimica Acta AG.