A novel bis(zinc-porphyrin)-oxoporphyrinogen donor-acceptor triad: Synthesis, electrochemical, computational and photochemical studies

The first example of a porphyrin-quinonoid donor-acceptor triad featuring (tetraphenylporphinato)zinc(II) moieties covalently attached to an oxoporphyrinogen through its macrocyclic nitrogen atoms is reported. This arrangement of chromophores results in an interesting interplay between the electron-donating zinc-porphyrin(s) and the electron/energy accepting oxoporphyrinogen. The optical absorption of the triad reveals features corresponding to both the donor and acceptor entities. The geometry and electronic structure of the triad deduced from B3LYP/3-21G((*)) calculations reveal an absence of inter-chromophoric interactions and localization of the HOMO on one zinc-porphyrin group and the LUMO on the oxoporphyrinogen scaffold. The electrochemical redox states of the triad were established from a comparative electrochemistry of the triad and the reference compounds. Both steady-state and time-resolved emission studies revealed quenching of the singlet excited state of zinc-porphyrin in the triad, and the free-energy calculations performed using Weller's approach indicate the possibility of electron transfer from the singlet excited zinc-porphyrin group to the oxoporphyrinogen in polar solvents. Time-resolved fluorescence studies reveal excited state energy transfer from zinc-porphyrin to oxoporphyrinogen in nonpolar solvents, while nanosecond transient absorption studies combined with time-resolved fluorescence studies in polar solvents are indicative of the occurrence of photoinduced charge separation from the singlet excited zinc-porphyrin to the oxoporphyrinogen. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)