Dissociative Intramolecular Charge Transfer after Local Two-Photon Ionization of Ferrocene Derivatives with Aromatic Chromophores

Experimental evidence for dissociative intramolecular charge transfer processes is found for gas-phase ferrocene-aniline derivatives after local ionization at the aniline chromophore site via intermediate states with predominant aniline character. The direct ionization at the ferrocene site can be excluded since there is a rapid dissociation of ferrocene in the intermediate state prior to ionization so that no ferrocene ions would be produced in this case. Because of the higher local ionization energy of the chromophore, charge transfer takes place after local ionization. The released energy and additional photon absorption leads to breaking of bonds and results in a dissociation into intact ferrocene or ferrocene-containing cations and neutral fragments.