Excitation-wavelength-dependent, ultrafast photoinduced electron transfer in bisferrocene/BF2-chelated-azadipyrromethene/fullerene tetrads

Abstract

Donor-acceptor distance, orientation, and photoexcitation wavelength are key factors in governing the efficiency and mechanism of electron-transfer reactions both in natural and synthetic systems. Although distance and orientation effects have been successfully demonstrated in simple donor-acceptor dyads, revealing excitation-wavelength-dependent photochemical properties demands multimodular, photosynthetic-reaction-center model compounds. Here, we successfully demonstrate donor- acceptor excitation-wavelength-dependent, ultrafast charge separation and charge recombination in newly synthesized, novel tetrads featuring bisferrocene, BF2 -chelated azadipyrromethene, and fullerene entities. The tetrads synthesized using multistep synthetic procedure revealed characteristic optical, redox, and photo reactivities of the individual components and featured "closely" and "distantly" positioned donor-acceptor systems. The near-IR-emitting BF2-chelated azadipyrromethene acted as a photosensitizing electron acceptor along with fullerene, while the ferrocene entities acted as electron donors. Both tetrads revealed excitation-wavelength-dependent, photoinduced, electron-transfer events as probed by femtosecond transient absorption spectroscopy. That is, formation of the Fc(+)-ADP-C60(.-) charge-separated state upon C60 excitation, and Fc(+)-ADP(.-)-C60 formation upon ADP excitation is demonstrated.