Photoinduced electron transfer in bisporphyin-diimide complexes

The bisporphyrin host ZnH was synthesized, and its complexation with two aromatic diimide guest molecules, bis(pyridyl)naphthalenediimide NIN and bis(pyridyl)phenyldiimide PIN, was investigated by 1H NMRand UV/Vis spectroscopy. The diimide guests were complexed simultaneously with both metalloporphyrins of the host, with association constants on the order of 10 8 M-1. The processes occurring in the complex after excitation of the porphyrinic host were studied by steady-state and time-resolved emission and transient absorption spectroscopy. Complexation alters the photophysical properties of the host ZnH; the luminescence bands shift to the red by 30 nm in the complexed forms, while the emission quantum yield and the lifetime decrease. Comparison of a complex between ZnH and a model guest unable to undergo photoinduced processes allowed us to establish that, in the diimide complexes, quenching of the porphyrinic luminescence occurs with a rate of 1.1x10 10 s-1. The process is identified as an electron transfer from the excited singlet of the porphyrinic host to the imide guest, which yields charge-separated states with a lifetime of 710 ps for ZnH+-NIN- and 260 ps for ZnH+-PIN-.