Dications of bis-triarylamino-[2.2]paracyclophanes: Evaluation of excited state couplings by GMH analysis

In this paper, we present the absorption properties of a series of bis-triarylamino-[2.2] paracyclophane diradical dications. The localized pi-pi* and the charge-transfer (CT) transitions of these dications are explained and analyzed by an exciton coupling model that also considers the photophysical properties of the "monomeric" triarylamine radical cations. Together with AMI-CISD-calculated transition moments, experimental transition moments and transition energies of the bis-triarylamine dications were used to calculate electronic couplings by a generalized Mulliken-Hush (GMH) approach. These couplings are a measure for interactions of the excited mixed-valence CT states. The modification of the diabatic states reveals similarities of the GMH three-level model and the exciton coupling model. Comparison of the two models shows that the transition moment between the excited mixed-valence states Yab of the dimer equals the dipole moment difference Delta mu((m))(ag) of the ground and the excited bridge state of the corresponding monomer.